1. Field of the Invention
The present invention concerns delay units of the type used for time-controlled initiation of energetic materials, for example, delay units of the type used in delay detonators, and methods of making such delay units.
2. Related Art
Conventional pyrotechnic delay units comprise a pulverulent pyrotechnic composition encased within a soft metal tube, such as a tube of lead or pewter. Such conventional delay units are typically placed within a detonator shell between the input signal from a fuse, such as shock tube, and the explosive output charge of the detonator. Detonation of the output explosive charge is delayed by the time it takes the length of pyrotechnic material to burn from its input to its output end. As is well known to those skilled in the art, it is necessary to very closely control the delay periods of individual detonators; typical delay periods range from 9 to 9,600 milliseconds or more, for example, 9, 25, 350, 500 and 1,000 milliseconds. Attainment of consistently accurate and precise delay times by burning of a column of pyrotechnic material is inherently limited, and the art is assiduously developing electronic delay units in order to increase delay time accuracy, despite the increased cost of electronic delay units as compared to pyrotechnic delay units.
International Application WO 2004/106268 A2 of Qinetiq Nanomaterials Limited for “Explosive Devices”, published 9 Dec. 2004, discloses explosive devices printed onto substrates from inks which may contain particles as small as 10 micrometers in diameter “for even . . . 0.1 micrometer or less in diameter.” (Page 4, lines 18-24.) Figures such as FIGS. 1 and 2 disclose serpentine or spiral patterns of printed explosive ink on a substrate. For example, there is described at page 15, lines 11-29, printing of the explosive ink in a single line which starts adjacent a heating element and terminates adjacent a secondary explosive material. The printed line of explosive ink initiates the secondary explosive. A zig-zag pattern may be used and will increase the delay time provided by the device.
The use of nanoporous iron oxide as the oxidizer component of propellants, explosives and pyrotechnic materials is known. See the article Aero-Sol-Gel Synthesis of Nanoporous Iron-Oxide Particles: A Potential Oxidizer For Nanoenergetic Materials, by Anand Prakash, Alon V. McCormick and Michael R. Zachariah, Chem. Mater. 2004, 16, 1466-1471, a publication of the American Chemical Society. The article describes the use of nanoparticles of a fuel such as aluminum and a metal oxide oxidizer, which react to liberate a large amount of energy. The high surface area per volume of material engendered by the very small particle sizes is stated to reduce mass-transfer limitations and achieve a chemical-kinetically controlled ignition. The oxidizer particles which are the subject of the invention are said to be in the 100 to 250 nanometer (“nm”) size range.
UK Patent Application 2 049 651 of Brock's Fireworks Limited, Dumfriesshire, Scotland discloses a process for applying a pyrotechnic or explosive composition to a surface by screen-printing the composition in the form of a liquid slurry or paste onto the surface allowing the composition thus obtained to dry and/or harden. It is disclosed that several layers may be applied, preferably, through a coarse mesh screen which allows relatively large solid particles to pass therethrough without becoming clogged. A size range of particles is not mentioned. It is further disclosed that several layers may be applied in the described manner and each layer may be the same or different. A final layer of inert material may be overprinted for purposes of waterproofing or to prevent ignition at the surface and, if desired, flocking may be applied between steps.
U.S. Pat. No. 6,712,917 issued Mar. 30, 2004 to Gash et al and entitled Inorganic Metal Oxide/Organic Polymer Nanocomposites and Methods Thereof discloses a method of producing hybrid inorganic/organic energetic nanocomposites.
U.S. Pat. No. 6,803,244 issued Oct. 12, 2004 to Diener et al and entitled Nanostructured Reactive Substance and Process For Producing the Same discloses a nanostructured reactive substance of, e.g., silicon and an oxidizing agent. The nanometer scale size of the particles, which are initially separated by a barrier layer, is said to permit virtually direct contact between the fuel and the oxidizing agent, once the barrier layer is broken open.
A detailed discussion of thermite mixtures, intermetallic reactants and fuels is contained in the paper Theoretical Energy Release of Thermites, Intermetallics, and Combustible Metals by S. H. Fischer and M. C. Grubelich, of Sandia National Laboratories, Albuquerque, N. Mex. The paper, SAND-98-1176C, was presented at the 24th International Pyrotechnics Seminar, Monterey, Calif. in July, 1998.
Generally, in accordance with the present invention there is provided a delay unit comprised of a substrate on which is deposited a timing strip and, optionally, a calibration strip, both of energetic material. As used herein and in the claims, an “energetic material” means an explosive, a pyrotechnic or other material which emits energy upon being initiated or ignited. The energetic material may be applied by ink compositions containing particles of the energetic material dispersed in a continuous liquid phase, and some or all of the energetic material particles may be nanosize particles. Optionally, the fuel and oxidizer components may be separately applied to the substrate as discrete fuel and oxidizer layers which contact or at least partly over-lie each other. The present invention also provides for printing on a substrate a timing strip of energetic material and printing on the same or another substrate a calibration strip of energetic material similar or identical to the energetic material of the timing strip, igniting the calibration strip and ascertaining its burn rate, and modifying the timing strip to adjust its burn time on the basis that the timing strip has the same burn rate as the calibration strip. The present invention thus provides for adjusting the burn time of energetic material timing strips in a manner analogous to the interrogation of electronic delay units to ascertain that they are properly programmed to provide the desired “burn time”, i.e., the desired delay period. The capability greatly enhances the delay period accuracy and precision of energetic material, e.g., pyrotechnic, delay units.
The present invention also provides for printing or otherwise depositing on a substrate an energetic material comprised of nanosize particles. Generally, the energetic material may comprise particles dispersed in a continuous liquid phase (“an ink”) and may be printed, e.g., in the form of timing strips and calibration strips, as described below. The ink is dried or allowed to dry, or hardens, into an adherent pattern on the substrate.
Specifically, in accordance with the present invention, there is provided a delay unit comprising a substrate having deposited thereon (a) at least one timing strip having a starting point and a discharge point and (b) a calibration strip, the timing strip and the calibration strip each comprising an energetic material, e.g., a fuel and an oxidizer, capable of conducting an energy-releasing reaction therealong, the calibration strip and the timing strip being separated from each other sufficiently to preclude ignition of the timing strip by the calibration strip. The energetic material may optionally comprise nanosize particles.
In one aspect of the present invention, the energetic material of at least the timing strip is comprised of at least one discrete layer of fuel and at least one discrete layer of oxidizer, one of the layer of fuel and one of the layer of oxidizer at least partly overlying the other.
In another aspect of the present invention, the energetic material of the calibration strip is substantially the same as the energetic material of the timing strip.
One aspect of the present invention provides a delay unit comprising a substrate having deposited thereon at least one timing strip having a starting point and a discharge point and comprising an energetic material capable of conducting an energy-releasing reaction therealong. The energetic material is selected from the class consisting of a fuel and an oxidizer and is comprised of at least one discrete layer of the fuel and at least one discrete layer of the oxidizer, the layer of the fuel and the layer of the oxidizer being in contact with each other.
Yet another aspect of the present invention provides that the timing strip comprises a first strip having a terminal gap, e.g., the first strip may be separated by the terminal gap from a second strip, and a bridging strip closing the terminal gap, e.g., by connecting the first strip to the second strip to close the terminal gap. The first strip, the optional second strip and the bridging strip cooperating to define the effective length of the timing strip between the starting point and the discharge point.
One aspect of the present invention provides a delay unit which further comprises at least one of (a) a pick-up charge in signal transfer communication with the starting point of the timing strip, and (b) a relay charge in signal transfer communication with the discharge point of the timing strip, and wherein a portion only of the timing strip is covered by at least one of the charges whereby the effective length of the timing strip is determined by placement of the charge or charges.
Other aspects of the present invention provide for a pick-up charge in signal transfer communication with the starting point of the timing strip and a relay charge in signal transfer communication with the discharge point of the timing strip. Optionally, a plurality of the timing strips may be connected in signal transfer communication at one end of the timing strips to the pick-up charge and at the other end of the timing strips to the relay charge, to provide redundant timing strips to initiate the relay charge.
In accordance with another aspect of the present invention, the timing strip is comprised of a major portion and a minor portion. The major portion has an effective length greater than that of the minor portion and the minor portion has a burn rate greater than that of the major portion. The disparity in the respective lengths and burn rates of the major and minor portions is great enough that the burn time of the minor portion is negligible compared to the burn time of the major portion so that the delay period of the delay unit is substantially determined by the burn time of the major portion.
A method aspect of the present invention provides for making a delay unit by steps comprising depositing onto a substrate a timing strip having a starting point and a discharge point, the timing strip comprising an energetic material comprised of at least one discrete layer of fuel and at least one discrete layer of oxidizer, with one of the layer of fuel and one of the layer of oxidizer at least partly overlying the other, and optionally further comprising depositing on the substrate a calibration strip of energetic material separated from the timing strip sufficiently to preclude ignition of the timing strip by the calibration strip.
Another method aspect of the invention provides for making a delay unit by a method comprising the following steps. (a) A timing strip having a starting point and a discharge point is deposited onto a substrate, the timing strip comprising an energetic material having a given burn rate along its length and the effective length of the timing strip being the continuous length along the timing strip between the starting point and the discharge point, the effective length and burn rate of the timing strip determining the delay period of the delay unit. (b) A calibration strip of given length having an initial point and a finish point is deposited onto the substrate, the calibration strip being comprised of an energetic material which is substantially identical to the energetic material of the timing strip. (c) The calibration strip is ignited and the time it takes for the calibration strip to burn from its initial point to its finish point is measured to thereby ascertain the burn rate of the calibration strip. (d) After carrying out step (c), the effective length of the timing strip is adjusted to attain a desired delay period on the basis that the burn rate of the timing strip is identical to the ascertained burn rate of the calibration strip.
Yet another method aspect of the invention provides for carrying out step (d) by providing one or more jump gaps in the timing strip, or by applying an accelerant to the timing strip, or by applying a retardant to the timing strip, or by applying one or both of a pick-up charge and a relay charge to cover a portion of the timing strip to leave an effective length of the timing strip between and uncovered by the charges, or by initially depositing only a portion of the timing strip by leaving at least one terminal gap between the starting point and discharge point of the timing strip and closing the gap or gaps in the timing strip with a bridging strip to provide a continuous timing strip from the starting point to the discharge point. The jump gap or gaps, the accelerant and the retardant are configured and constituted to provide a desired burn rate for the adjusted timing strip which, based on the burn rate ascertained for the calibration strip, will provide a desired delay period for the delay unit. Similarly, the bridging strip is configured and constituted and the pick-up and/or relay charges are positioned to provide the timing strip with an effective length which, at the burn rate ascertained for the calibration strip, will provide a desired delay period for the delay unit.
Various aspects of the present invention provide that the energetic material contains nanosize particles or the particles consist essentially of nanosize particles. The energetic material used in the methods of the invention may comprise a fuel and an oxidizer and the deposited energetic material may be comprised of at least one discrete layer of fuel and at least one discrete layer of oxidizer, one of the layer of fuel and the layer of oxidizer at least partly overlying the other.
Generally, at least one of the components of the energetic material is comprised of particles which may be a “nanosize” material, such as a “nanoenergetic material”, e.g., a “nanopyrotechnic material”; such terms as used herein denote a particle diameter size range of from about 20 to about 1,500 nanometers (“nm”), or any suitable size range less than, but lying within, the broad range of about 20 to about 1,500 nm. For example, the particle diameter size range may be from about 40 to about 1,000 nm, or from about 50 to about 500 nm, or from about 60 to about 200 nm, or from about 80 to about 120 nm, or from about 20 to 100 nm. The exceedingly small size of particles, e.g., nanosize particles, promotes good reaction because of the intimate contact between reactive particles and enables the formation of strips having very small critical diameters. That is, strips of very small cross-sectional area are capable of sustaining reaction along their length, because of the particles of energetic material being of such small size, e.g., nanosize.
Unless specifically otherwise stated, or unless the context clearly requires otherwise, the following descriptions apply equally to methods and structures which comprise (1) energetic material deposited as a mixture of fuel and oxidizer, and (2) energetic material whose fuel and oxidizer components are deposited separately. When separate layers of fuel and oxidizer are applied, it is immaterial which of the fuel and oxidizer layers is first applied onto the substrate. That is, either the fuel or oxidizer layer may be the top layer, and two or more alternating layers of, respectively, fuel and oxidizer may be applied, or the separate layers may simply contact each other.
The energetic material may comprise a pyrotechnic material comprised of a fuel and an oxidizer; for example, the pyrotechnic material may, but need not necessarily, comprise a thermite material. The energetic material may be applied by printing with inks of energetic material which harden or dry on the substrate. Both fuel and oxidizer particles may be dispersed in the continuous liquid phase of a single ink. Alternatively, one ink may comprise nanosized fuel particles dispersed in a continuous liquid phase, and the other ink may comprise nanosized oxidizer particles dispersed in a continuous liquid phase. Only one of the fuel particles and oxidizer particles, or only some of the particles of each, or all the particles may be nanosized particles. At least one of the energetic material components may have a nano sol-gel structure, such as a sol-gel of nanoporous iron oxide.
Referring to
Substrate 12 may be made of any suitable material such as conventional printed circuit board, a fiberglass-reinforced plastic, a ceramic, or any suitable material or combination of materials. For example, the substrate may comprise an electrically non-conductive material, or a material having an electrically non-conductive surface layer on which the timing strip and, optionally, a calibration strip (as described below) are printed. Substrate 12 may optionally be made of an energetic material or it may have a coating of energetic material on the surface (sometimes below referred to as “the active surface”) upon which the various strips are deposited. A “reactive” substrate or coating as used herein means a substrate or coating which participates in the burn reaction of the strip or strips of energetic material. For example, a substrate or coating which supplies oxygen to the burn reaction, such as an oxygen-containing metal compound, e.g., potassium nitrate, would be a reactive substrate or coating.
A significant advantage of the present invention is that it enables adjusting the timing strip, such as timing strip 14, based on the result attained by functioning the calibration strip, such as calibration strip 20. This adjustment may be carried out in a number of different ways as described below in connection with certain of the Figures. Generally, adjusting the timing strip may comprise one or more of adding to it an accelerant or a decelerant to either increase or decrease the burn rate of the timing strip; providing one or more jump gaps in the timing strip to slow down the burn rate, adjusting the effective length of the timing strip either by initially applying only a portion of the timing strip and completing the timing strip so as to impart to it a selected effective length based on the burn rate as determined by functioning the calibration strip or positioning one or both of charges, such as charges 16 and 18 described below, to leave between them a desired uncovered (by the charges) effective length of the timing strip.
Timing strip 14 has a starting point 14d and a discharge point 14e. The “effective length” of a timing strip is the continuous length along the timing strip between its starting point and discharge point. Thus, the effective length of timing strip 14 starts at starting point 14d, traverses a portion of first strip 14a to a first intersection point I1 with bridging strip 14c, traverses a portion of bridging strip 14c to a second intersection point I2 with second strip 14b, and then traverses that portion of second strip 14b between the second intersection point 12 and discharge point 14e. It is seen that terminal portions of strips 14a and 14b are excluded from the effective length of timing strip 14 because of the particular location of intersection points I1 and I2 in the illustrated embodiment. Similarly, terminal ends of bridging strip 14c are excluded from the effective length of timing strip 14 because they extend slightly beyond the first and second intersection in order to insure a good connection between bridging strip 14c and strips 14a and 14b.
Starting point 14d is connected in signal transfer communication to a pick-up charge 16 disposed on substrate 12, and discharge point 14e is in signal transfer communication with a relay charge 18 also disposed on substrate 12. Pick-up charge 16 and relay charge 18 may be printed on substrate 12 in a manner similar or identical to that used to print timing strip 14 and calibration strip 20. Alternatively, charges 16 and 18 may be applied to substrate 12 by any other suitable means. Charges 16 and 18 may, but need not, be comprised of energetic nano materials.
In the various embodiments of the invention, the timing strip is deposited on the substrate and has a starting point which is positioned to receive an input signal, and a discharge point which is spaced from the starting point and positioned to initiate an output signal. The length of the timing strip between the starting point and the discharge point, i.e., the longitudinal distance along the timing strip between its starting and discharge points, is its effective length; the burn time of the effective length of the timing strip determines the time delay between the timing strip's receipt of the input signal and its initiation of the output signal. The timing strip may be configured in a straight, curved, zig-zag or other pattern, to provide a desired effective length of the timing strip. The substrate may optionally be a reactive substrate which participates in or contributes to the reaction of the energetic material in the timing strip (and, optionally, in a calibration strip, as described below).
Generally, the pick-up charge at the starting point of the timing strip is in signal transfer relationship with the output of a signal transmission fuse, and the relay charge at the discharge point of the timing strip is in signal transfer communication with an output explosive charge of an explosive device, such as a delay detonator, incorporating the delay unit of the invention. Thus, generally, one or both of: (1) a pick-up charge is disposed in signal transfer communication between the output of a signal transmission fuse and the starting point of the timing strip, and (2) a relay charge is disposed in signal transfer communication with the discharge point of the timing strip. The pick-up and relay charges may be deposited on the substrate by printing or any other suitable means.
The saw-tooth configuration of some of the strips is used simply to provide a longer effective length of strip within the limited area provided by substrate 12. Obviously, any suitable pattern of strips (spiral, serpentine, etc.) may be utilized. Substrate 12 may, of course, be of any size suitable for the intended use of the delay unit. For a delay unit which is intended for use in a standard size detonator shell, as described below, substrate 12 would typically have a width selected to approximate the inside diameter of the detonator shell so as to fit snugly therein. A mounting frame (not shown in the drawings) sized to snugly fit within the detonator shell may optionally be utilized to support the substrate 12 which would be appropriately sized to fit the mounting frame. Substrate 12 would typically have a length of from about one-quarter inch (0.64 cm) to about 1.2 inches (3.05 cm) to easily fit within a standard size detonator shell. Substrate 12, which may be made of conventional printed circuit board, need be only thick enough to provide sufficient rigidity and mechanical strength to be manipulated during manufacture and installation in an explosive device without physical distortion of the strips on the active surface. For example, substrate 12 may be from about 1/16 to ⅛ inch (0.159 to 0.318 cm) thick. Arrows S and E in
Delay unit 10 may be manufactured by the following method. A suitable substrate 12 has printed (or otherwise applied) thereon first strip 14a, second strip 14b and calibration strip 20. A terminal gap is left between strips 14a and 14b. Strips 14a, 14b and 20 (sometimes, with a bridging strip, collectively referred to below as “the applied strips”) are all printed or otherwise applied from the same batch of ink or from identical batches of ink. Start flash charge 22 and finish flash charge 24 may be printed or otherwise applied to substrate 12 by any suitable means and may, but need not, be applied to substrate 12 simultaneously with the application of strips 14a, 14b and 20. Pick-up charge 16 and relay charge 18 are applied to the active surface of substrate 12 by any suitable means. Charges 16, 18, 22 and 24 may, but need not, be comprised of nanosized materials.
Delay unit 10 may be subjected to a test unit which ignites start flash charge 22. An accurate reading of the time period required for calibration strip 20 to burn and ignite finish flash charge 24 is taken by any suitable measuring device. The time period required for calibration strip 20 to burn from charge 22 at the initial point of calibration strip 20 to charge 24 at the finish point of calibration strip 20 is, for example, readily read electronically by measuring the time delay between the two flashes engendered by charges 22 and 24. That measured time interval and the known length of calibration strip 20 enables ready calculation of the burn rate (distance per unit time, e.g., centimeters per second) of calibration strip 20. The burn rate of calibration strip 20 will be substantially identical to the burn rate of timing strip 14 because timing strip 14 is printed from the same or identical batches of energetic material ink as calibration strip 20 and, preferably, during the same manufacturing operation and under the same printing conditions. Preferably, the timing and calibration strips are of identical thickness and width and are disposed on the same substrate or on identical substrate material, to promote burning of the timing strip 14 and calibration strip 20 at substantially identical rates. In other embodiments, the entirety of timing strip 14 is made from the same energetic material ink as used for calibration strip 20.
Once the burn rate is known, i.e., the speed of travel of the signal along the timing strip 14, the configuration of a bridging strip 14c and its points of intersection with first strip 14a and second strip 14b may be selected so that the effective length of the burn from starting point 14d to discharge point 14e yields the desired delay period for delay unit 10. Bridging strip 14c is applied after application of strips 14a and 14c in cases where calibration strip 20 is to be used to determine the effective length of timing strip 14. Once that is determined, subsequent delay units 10 may be made by applying strips 14a, 14b and 14c without using calibration strip 20. Therefore, strips 14a, 14b and 14c may be applied simultaneously or in any desired order. Calibration strip 20 may be used when new batches of energetic material inks are used, or at specified intervals as a quality control check. The effective length of the timing strip 14 which is needed to provide a specific delay period is accurately determined by the destructive testing of the calibration strip 20.
After the applied strips and charges dry or harden, any desired post-printing treatment or processing of delay unit 10, such as the optional application of a lacquer, a laminate or other coating to “the active surface” (the surface of substrate 12 to which the strips are applied), may be carried out. Alternatively, or in addition, a potting compound may be used to enclose the timing strip 14 or portions thereof, and/or charges 16 and 18. The optional laminate or coating may be inert to the burn reaction or it may comprise an oxidizer or a fuel or both which participate in the burn reaction of the printed strips. For example, alternate layers of a fuel and oxidizer may be applied as a coating over the applied strips. In one embodiment, an oxidizer layer may be applied directly over the applied strips, overlain by a fuel layer which in turn is overlain by another oxidizer layer. Specific oxidizers and fuels usable in the applied strips and in the optional coating layers are described below. Oxidizer and/or fuel coating layers (“reactive layer(s)”) may be applied with a discontinuity between the reactive layer(s) overlying calibration strip 20 and those overlying timing strip 14, in order to insure that ignition of calibration strip 20 does not also ignite timing strip 14.
The timing strip 14 and the calibration strip 20 may be applied to substrate 12 by any suitable printing or deposition technique such as those used in the printing and graphics industries. These include, by way of illustration and not limitation, silk screening, ink-jet printing, stenciling, transfer printing, gravure printing and other such techniques.
The illustrated embodiment of
It will be appreciated that numerous variations may be made to the strip pattern illustrated in
In some embodiments, a portion of timing strip 14, e.g., bridging strip 14c and, optionally, second strip 14b, may comprise an energetic material which burns at a substantially faster rate than does first strip 14a. In this arrangement, the faster-burning strip or strips are made as short as is feasible and their composition is selected to burn at as high a rate as is feasible, so that the total burn time of the effective length of the faster-burning strip or strips is negligible compared to the burn time of first strip 14a. The calculations for the configuration and placement of bridging strip 14c are thereby simplified, because only the effective length of first strip 14a which will yield the desired delay time must be taken into account. For example, referring to
As is well-known to those skilled in the art, an initiation device (not shown) ignites the energetic material contained within shock tube 32. The resulting input signal (represented in
The delay unit of the present invention may be inserted within a conventional detonator shell 28 (
As noted above, the processing requirements of conventional pyrotechnic delay elements include filling a lead or pewter tube with a pyrotechnic composition and drawing the tube down to a significantly reduced diameter. This involved processing step is omitted by the practices of the present invention, which require only a printing operation to make the pyrotechnic delay. The present invention thus significantly reduces material requirements and processing requirements, while providing pyrotechnic delays of greatly enhanced accuracy.
The present invention also provides the option of providing and utilizing a calibration strip on the substrate to further enhance the accuracy of delay times provided by timing strip 14. The calibration strip may be deposited on the same substrate on which the timing strip is deposited, or it may be deposited on a separate, test substrate. The timing strip and calibration strip may be deposited from the same ink or inks at about the same time and under the same or similar conditions to help insure that they have the same, or nearly the same, burn rate. Optionally, at least one, and preferably both, of the timing strip and the optional calibration strip are applied as discrete layers of fuel and oxidizer. Despite taking the greatest care in preparing energetic materials, including energetic inks as contemplated by the present invention, variations nonetheless occur from batch to batch. The provision of a calibration strip which is substantially identical to all or part of the timing strip, and use of the calibration strip during the manufacturing process to time the burn rate along the calibration strip and configure the timing strip accordingly, enables extremely close control and reproducibility of a desired delay period. This advantage is not available to conventional pyrotechnic delays and manufacturing techniques.
Referring now to
Referring again to
The practices of the present invention provide the highly advantageous ability to adjust each timing strip to provide a closely controlled accurate and precise burn time and consequent delay period. Such individual adjustment has previously been available only with more expensive electronic delay units. In some circumstances, however, it may be desired to test only representative samples of a given production run by ignition of calibration strip 20. For example, one in ten, one in fifty or one in one hundred of the substrates 12 may be tested by ignition of calibration strip 20. The frequency at which the substrates or delay units are tested will be shown by experience in a given manufacturing operation to provide the required degree of control of the accuracy and precision of the delay units provided by the particular manufacturing process and materials utilized. Naturally, testing of each unit provides the maximum degree of quality control for accuracy and precision of the delay period.
The nanosized materials used in this Example are all commercially-available materials supplied by Nanotechnologies Inc. of Austin, Tex. Mixing of the nanosized materials with a liquid was carried out by placing the nanosized materials and the liquid in stainless steel beakers and inserting into the mixture an ultrasonic horn which was operated intermittently with equal duration on-and off periods with the beaker being rotated about the horn. Mixing was conducted for about fourteen minutes while the temperature of the mixture was raised by the ultrasonic mixing from about 19° C. to about 45° C. The mixture was then decanted onto a stainless steel pan to form a thin film on the pan, which was heated at 70° for 1½ hours. The resulting dried material was flaked off the pan with a brush and collected. The collected dried material was then blended into a nitrocellulose lacquer in each case, as follows.
0.18 milliliters (ml) of n-butyl acetate
0.13 ml of nitrocellulose lacquer
0.24 grams of the collected dried material
The combined materials were mechanically thoroughly mixed and placed into a plastic syringe filled with a needle tip having a cannula diameter of 0.0052 inch (0.1321 millimeter).
The resulting “ink” was applied through the needle tip onto a clean aluminum plate in straight-line and squiggle (wavy) line patterns. The applied lines were allowed to thoroughly dry, by evaporation of the volatile components of the lacquer.
Sample 1A
Nanosized materials:
Nanosized materials:
Referring to
Timing strip 114 has a starting point 114c and a discharge point 114d, the distance between those two points defining the “effective length” of timing strip 114. Starting point 114c is connected in signal transfer communication to a pick-up charge 116 disposed on substrate 112, and discharge point 114d is in signal transfer communication with a relay charge 118 also disposed on substrate 112. Pick-up charge 116 and relay charge 118 may be applied to substrate 112 in a manner similar or identical to that used to print or otherwise apply timing strip 114 to substrate 112. Alternatively, charges 116 and 118 may be applied to substrate 112 by any other suitable means. Charges 116 and 118 may, but need not, be comprised of energetic nanosize materials, or they may be comprised of conventional explosive materials.
Application of fuel layer 114a and oxidizer layer 114b in separate operations provides an important safety advantage as it avoids the necessity for mixing fuel and oxidizer components into a single ink and then handling the resulting energetic material and applying it to substrate 112. By applying the fuel and oxidizer components separately, a safer and less expensive operation may be employed as compared to handling a pre-mixed reactive composition. Separate application of the fuel and oxidizer obviates the need for certain precautions which are necessary when handling reactive mixtures of fuel and oxidizer. Such precautions include employing explosion barricades, maintaining temperature and humidity conditions which will reduce the likelihood of inadvertent ignition of the reactive mixture, and taking precautions to prevent electrostatic discharge which might ignite the reactive mixture.
Substrate 112 may be made of any suitable material such as conventional printed circuit board, a fiberglass-reinforced plastic, a ceramic, or any suitable material or combination of materials. For example, the substrate may comprise an electrically non-conductive material, or a material having an electrically non-conductive surface layer on which the timing strip 114 and, optionally, a calibration strip (as described below) are printed. Substrate 112 may optionally be made of an energetic material or it may have a coating of energetic material on the surface (sometimes below referred to as “the active surface”) upon which the timing strip, optional calibration strip and pick-up and relay charges (described below) are deposited. A “reactive” substrate or coating as used herein means a substrate or coating which participates in the burn reaction of the strip or strips of energetic material. For example, a substrate or coating on active surface 112a which supplies oxygen to the burn reaction of the timing strip or calibration strip, such as an oxygen-containing metal compound, e.g., potassium nitrate, would be a reactive substrate or coating.
Substrate 112 may, of course, be of any size suitable for the intended use of the delay unit. For a delay unit which is intended for use in a standard size detonator shell, as described below, substrate 112 would typically have a width selected to approximate the inside diameter of the detonator shell so as to fit snugly therein. A mounting frame (not shown in the drawings) sized to snugly fit within the detonator shell may optionally be utilized and the substrate 112 would then be sized to fit the mounting frame. Substrate 112 would have a length of from about one-quarter inch (0.64 cm) to about 1.2 inches (3.05 cm) to easily fit within a standard size detonator shell. Substrate 112, which may be made of conventional printed circuit board, need be only thick enough to provide sufficient rigidity and mechanical strength to be manipulated during manufacture and installation in an explosive device without physical distortion of the strips on the active surface. For example, substrate 112 may be from about 1/16 to ⅛ inch (0.159 to 0.318 cm) thick. Arrows S and E in
Delay unit 110 may be manufactured by the following method. A suitable substrate 112 has printed (or otherwise applied) thereon timing strip 114. Pick-up charge 116 and relay charge 118 are applied to the active surface 112a of substrate 112 by any suitable means. After the applied timing strip 114 and charges 116, 118 dry, any desired post-printing treatment or processing of delay unit 110, such as the optional application of a lacquer, a laminate or other coating to the active surface 112a, may be carried out. Alternatively, or in addition, a potting compound may be used to enclose the timing strip 114 or portions thereof, and/or charges 116 and 118. The optional laminate or coating may be inert to the burn reaction or it may comprise an oxidizer or a fuel or both which participate in the burn reaction of the timing strip 114.
Referring now to
Also disposed on active surface 212a is a calibration strip 120 which itself is comprised of a plurality of fuel layers 214a and oxidizer layers 214b arranged identically to the alternating fuel and oxidizer layers 214a and 214b of timing strip 214. Consequently, calibration strip 120 is of similar, preferably identical, composition and structure as timing strip 214, except that calibration strip 120 may, of course, have an effective length which is shorter or longer than the effective length of timing strip 214 without any disadvantage. Preferably, the alternating layers of calibration strip 120 are applied from the same batches of inks as are the layers of timing strip 214 and, preferably, the layers of calibration strip 120 are applied at the same time and under the same conditions as those of timing strip 214. Calibration strip 120 has a calibration starting point 120a and a calibration discharge point 120b, which points are in signal transfer contact with, respectively, start flash charge 122 and finish flash charge 124. While calibration strip 120 is illustrated as being applied to the same substrate 212 as timing strip 214, it may be applied to a separate substrate (not shown) to prepare a test piece for testing as described below. The separate test piece substrate is preferably of similar or identical composition as substrate 212.
Starting point 214c of timing strip 214 is in signal transfer communication with pick-up charge 216 and discharge point 214d of timing strip 214 is in signal transfer communication with relay charge 218. Calibration strip 120 and its associated flash charges 122, 124 are separated from timing strip 214 and its associated charges 216, 218 so that ignition of calibration strip 120 and its associated charges will not ignite timing strip 214 and its associated charges.
Delay unit 210 (or a separate test piece, not shown, having calibration strip 120 and its associated charges 122, 124 thereon) may be subjected to testing in a test unit. The test unit ignites start flash charge 122 and takes an accurate reading of the time period required for calibration strip 120 to burn and ignite finish flash charge 124. This may be accomplished by any suitable measuring device. The time period required for calibration strip 120 to burn from charge 122 to charge 124 is, for example, readily read electronically by measuring the time delay between the two flashes engendered by charges 122 and 124. That measured time interval and the known length of calibration strip 120 enables ready calculation of the burn rate (distance per unit time, e.g., centimeters per second) of calibration strip 120. The burn rate of calibration strip 120 will be substantially identical to the burn rate of timing strip 214 because timing strip 214 is preferably printed from the same or identical batches of energetic material component inks as calibration strip 120 and, preferably, during the same manufacturing operation and under the same printing conditions. Preferably, the timing and calibration strips are of identical thickness, width and configuration of layers and are disposed on the same substrate or on identical substrate material. All this is to promote burning of the timing strip 214 and calibration strip 120 at substantially identical rates.
Once the burn rate, i.e., the speed of travel of the signal along calibration strip 120, is known, the effective length of timing strip 214 required for a desired delay period is determined on the basis that timing strip 214 has the same burn rate as calibration strip 120. Calibration strip 120 may thus be utilized as a quality control check if timing strip 214 has already been applied to substrate 212. In other instances, calibration strip 120 may be used to determine the length of timing strip 214. As noted above, each or only selected ones of the delay units being manufactured, may be tested to assure maintaining the time delay period within desired limits. As also noted above, charges 216, 218 may be applied onto a pre-existing timing strip 214 which is made somewhat longer than required for the desired time delay period. Charges 216 and 218 are placed on timing strip 214 at a selected distance from each other to provide an effective length of timing strip 214 uncovered by and between charges 216 and 218 which, based on the burn rate determined by use of calibration strip 120, will give the desired delay period.
The timing strips 114, 214 and the calibration strips 120 may be applied to substrates 112, 212 by any suitable printing or deposition technique such as those used in the printing and graphics industries. These include, by way of illustration and not limitation, silk screening, ink-jet printing, stenciling, transfer printing and other such techniques.
The delay unit of the present invention may be inserted within a conventional detonator shell 128 (
A delay unit as described above may be encapsulated within any suitable encapsulation material, such as a potting compound of the type typically used to encase electronic components. The encapsulating material may be configured to provide a suitable shape and size for a desired purpose. For example, if the delay unit is intended for use within a delay detonator of conventional size, the encapsulating material is formed as a cylinder of circular cross section whose outside diameter snugly fits within the inside diameter of a standard detonator shell. Suitable passageways are formed within the encapsulating material in order to permit input and output signals from the delay unit.
Alternatively, the encapsulating material may comprise simply a layer or laminate of any suitable non-reactive material deposited over the top of the timing strip; this layer may be deposited by spraying, roll application, painting, printing, application of a laminate sheet or other suitable techniques for applying such laminate coatings.
Encapsulation of the delay unit can serve several purposes, including isolating the timing strip from environmental effects such as the pressure pulse from a shock tube (which may affect the burn speed of the timing strip), enabling the delay fuze element consisting of the timing strip on the substrate to conform to the shape of a container or package such as a standard detonator shell, and preventing short-circuiting or flashing over by the delay fuze component by the end spit (the flame pulse signal) from a shock tube.
Cylindrical embedment 158 has an inlet passage 160 formed at inlet end 158a thereof and an outlet passage 162 formed at outlet end 158b thereof. Inlet passage 162 extends longitudinally along embedment 158 sufficiently far to expose pick-up charge 716 to an input signal indicated by the arrow S. Outlet passage 162 extends longitudinally along embedment 158 from outlet end 158b thereof sufficiently far that the signal generated by relay charge 718 will emerge from embedment 158 as indicated by the arrow E.
Embedment 158 may be substituted for delay unit 210 in the detonator illustrated in
The cylindrical configuration of embedment 158 is dimensioned to have an outside diameter d (
As seen in
While, as noted above, a cylindrical configuration of embedment 158 is well suited for use within a cylindrical detonator shell such as shell 128, the embedment obviously may take other suitable shapes, whether for use in circular or non-circular cross section devices. Even when used within detonator shell 128, as shown in
The most common fuels for nanoenergetic materials used in the delay units of the present invention are Al, Cu and Ag, primarily for the reasons that they are highly conductive, are relatively cheap, have proven to be safe to work with as “nanosize” (about 20 to about 1,500 nm) diameter particles, and offer good performance. Generally, fuel and oxidant reactant pairs useful in nanosize particles for applying timing and calibration strips in accordance with the teachings of the present invention are M′+MxOy, where M′ is a suitable metal fuel and M is a suitable metal different from M′ and in oxide form, and x and y are positive integers, e.g., 1, 2, 3 . . . n, which may be the same or different. Both M′ and MxOy must be capable of being reduced to nanosize particles. Suitable metal fuels in nanosize particles in accordance with the practices of the present invention include Ag, Al, B, Cu, Hf, Si, Sn, Ta, W, Y and Zr. Known nanosize thermites include the following stoichiometric fuel and oxidant reactant pairs, which are taken from those listed in Table 1a of the above-described paper Theoretical Energy Release of Thermites, Intermetallics and Combustible Metals (“the Sandia Paper”). The following specific reactant pairs are believed to be suitable for the practices of the present invention. Stoichiometric ratios of the fuel and oxide are shown; the practices of the present invention may, but need not, employ stoichiometric ratios of the fuel and oxidizer.
2Al+3AgO; 2Al+3Ag2O; 2Al+B2O3; 2Al+Bi2O3; 2Al+3CoO; 8Al+3Co3O4; 2Al+Cr2O3; 2Al+3CuO; 2Al+3Cu2O; 2Al+Fe2O3; 8Al+3Fe3O4; 2Al+3HgO; 10Al+3I2O5; 4Al+3MnO2; 2Al+MoO3; 10Al+3Nb2O5; 2Al+3NiO; 2Al+Ni2O3; 2Al+3PbO; 4Al+3PbO2; 8Al+3Pb3O4; 2Al+3PdO; 4Al+3SiO2; 2Al+3SnO; 4Al+3SnO2; 10Al+3Ta2O5; 4Al+3TiO2; 16Al+3U3O8; 10Al+3V2O5; 4Al+3WO2; 2Al+WO3; 2B+Cr2O3; 2B+3CuO; 2B+Fe2O3; 8B+3Fe3O4; 4B+3MnO2; 8B+3Pb3O4; 3Hf+2B2O3; 3Hf+2Cr2O3; Hf+2CuO; 3Hf+2Fe2O3; 2Hf+Fe3O4; Hf+MnO2; 2Hf+Pb3O4; Hf+SiO2; 2La+3AgO; 2La+3CuO; 2La+Fe2O3; 2La+3HgO; 10La+3I2O5; 4La+3MnO2; 2La+3PbO; 4La+3PbO2; 8La+3Pb3O4; 2La+3PdO; 4La+3WO2; 2La+WO3; 3Mg+B2O3; 3Mg+Cr2O3; Mg+CuO; 3Mg+Fe2O3; 4Mg+Fe3O4; 2Mg+MnO2; 4Mg+Pb3O4; 2Mg+SiO2; 2Nd+3AgO; 2Nd+3CuO; 2Nd+3HgO; 10Nd+3I2O5; 4Nd+3MnO2; 4Nd+3PbO2; 8Nd+3Pb3O4; 2Nd+3PdO; 4Nd+3WO2; 2Nd+WO3; 2Ta+5AgO; 2Ta+5CuO; 6Ta+5Fe2O3; 2Ta+5HgO; 2Ta+I2O5; 2Ta+5PbO; 4Ta+5PbO2; 8Ta+5Pb3O4; 2Ta+5PdO; 4Ta+5WO2; 6Ta+5WO3; 3Th+2B2O3; 3Th+Cr2O3; Th+2CuO; 3Th+2Fe2O3; 2Th+Fe3O4; Th+MnO2; Th+PbO2; 2Th+Pb3O4; Th+SiO2; 3Ti+2B2O3; 3Ti+2Cr2O3; Ti+2CuO; 3Ti+2Fe2O3; Ti+Fe3O4; Ti+MnO2; 2Ti+Pb3O4; Ti+SiO2; 2Y+3CuO; 8Y+3Fe3O4; 10Y+3I2O5; 4Y+3MnO2; 2Y+MoO3; 2Y+Ni2O3; 4Y+3PbO2; 2Y+3PdO; 4Y+3SnO2; 10Y+3Ta2O5; 10Y+3V2O5; 2Y+WO3; 3Zr+2B2O3; 3Zr+2Cr2O3; Zr+2CuO; 3Zr+2Fe2O3; 2Zr+Fe3O4; Zr+MnO2; 2Zr+Pb3O4; and Zr+SiO2.
The following metal oxides taken from Table 3a of the Sandia Paper are believed to be suitable in nanosize particles for use as oxidizers in the practices of the present invention.
Ag2O; Al2O3; B2O3; BeO; Bi2O3; Ce2O3; CoO; Cr2O3; Cs2O; Cs2O3; CsO2; CuO; Cu2O; Fe2O3; Fe3O4; HfO2; La2O3; Li2O; MgO; Mn3O4; MoO3; Nb2O5; Nd2O3; NiO; Pb3O4; PdO; Pt3O4; SiO2; SnO2; SrO2; Ta2O5; ThO2; TiO2; U3O8; V2O5; WO2; WO3; Y2O3; ZnO; and ZrO2.
In addition to the above known metal and metal oxide fuel and oxidizer reactant pairs, TiO2, not heretofore known as a suitable oxidizer for nanosize particle thermite compositions, works well in the practices of the present invention, especially when used in combination with Al as the metal fuel.
In those cases in which the oxidizer and fuel components are maintained separately from each other and applied to the substrate separately, the application is carried out in a manner which places the separately applied fuel and oxide layers into contact with each other on the substrate. Contact may be abutting contact, peripherally overlapping contact or fully overlying contact, i.e., one layer applied over and fully covering another. Two or more alternating layers of fuel and oxidizer materials, e.g., nanosized fuel and oxidizer materials in both the fuel and oxidizer layers, may be employed. As described elsewhere herein, gaps may be provided in the energetic material to increase the burn time in a particular case.
The order of application of the fuel and oxidizer layers to the substrate is not critical, i.e., the oxidizer layer may be the first layer deposited and the fuel layer may be deposited over the oxidizer layer.
As is well-known to those skilled in the art, an initiation device (not shown) ignites the energetic material contained within shock tube 132. The resulting input signal, represented in
The oxidizer and fuel components of the energetic material may be separately applied to the substrate in a pattern which places the separately applied coatings of oxidizer and fuel in contact with each other on the substrate. Thus,
Referring now to
The present invention enjoys significant advantages over conventional pyrotechnic delay units. For one, the printed or otherwise deposited strips of the present invention require a much smaller quantity of energetic material as compared to the quantity of pyrotechnic material required for a conventional pyrotechnic-filled metal tube providing the same delay period. The significant reduction in the quantity of energetic material attainable with the present invention not only reduces material costs, but ameliorates or overcomes the problem of gassing. The formation of the gaseous products of combustion of the energetic material of a delay unit creates a pressure within the delay unit or its enclosure, which pressure increase affects the burn rate, thereby adversely affecting accuracy and reliability in attaining the desired delay time. The use of very small quantities of energetic materials in the practices of the present invention as compared to conventional pyrotechnic delay tubes drastically reduces the amount of gaseous reaction products, even if a gas-generating pyrotechnic composition is used as the nanoenergetic material. Further, the present invention also includes the use of thermite materials as the nanopyrotechnic material, and thermite materials do not generate significant (or any) gaseous products of combustion.
The present invention also provides the option of providing and utilizing a calibration strip on the substrate to further enhance the accuracy of delay times provided by timing strip 114. Despite taking the greatest care in preparing energetic materials, including fuel and oxidizer inks as contemplated by the present invention, variations nonetheless occur from batch to batch. The provision of a calibration strip which is substantially identical to all or part of the timing strip, and use of the calibration strip during the manufacturing process to time the burn rate along the calibration strip and configure the timing strip accordingly, enables extremely close control and reproducibility of a desired delay period. This advantage is not available to conventional pyrotechnic delays and manufacturing techniques.
Referring now to FIGS. 11 and 11A-11C, there is shown schematically another embodiment of a production line for manufacturing an embodiment of the delay units of the invention and the resulting product. The embodiment of
In the illustrated embodiment, first strip 614x is of saw-tooth configuration in order to increase its effective length and, thereby, its burn time whereas strip 614y is straight. The calibration strip 620 (
As with the other embodiments, calibration strip 620 and timing strip 614 are applied in separate steps to apply the fuel and oxidizer components of calibration strips 620 and the strips of timing strip 614 separately. Calibration strip 620 and timing strip 614 are preferably made of identical materials and configured identically with respect to the number and order of layers of fuel and oxidizer in order that their respective burn rates be substantially identical.
After leaving the first pair of printing heads 148a, 148b, substrate 612, with strips 614x, 614y and 620 applied, e.g., printed, on the active surface 612a thereof, passes through a drying oven 150 in which the applied strips are thoroughly dried.
Typically, an optical reader will measure the time between the flash engendered by ignition of calibration start flash charge 622 and calibration finish flash charge 624. That datum is recorded at test station 152. The recorded datum is utilized to calculate the burn rate of calibration strip 620 and, assuming the same burn rate for the effective length of timing strip 614 (
As noted above, not every one of the delay units has to be tested by ignition of its associated or test calibration strip. For example, one in ten, one in fifty or one in one hundred of the delay units may be tested by ignition of an associated or test calibration strip. The frequency at which the substrates or delay units are tested will be shown by experience in a given manufacturing operation to provide the required degree of control of the accuracy of the delay units provided by the particular manufacturing process and materials utilized.
In some embodiments of the present invention, the timing strip is interrupted, that is, gaps are provided in it, in order to modify its timing characteristics. These gaps are small enough so that the signal will jump over the gaps and travel from the starting point to the discharge point. In the case of separately applied fuel and oxidizer layers, this can be done by interrupting both the fuel and oxidizer layers or just one of the layers, for example, the oxidizer layer, while leaving the fuel layer continuous. This aspect of the invention is not limited to providing a simple gap in the timing strip, but the gap or gaps could be of any suitable geometry. For example, the gap or gaps may be provided in chevron-shaped, convoluted, or other suitable patterns.
Referring now to
As indicated above, the regular sized and spaced gaps 164 are but one embodiment of jump gaps in the timing strip. The jump gaps could be differently sized, irregularly spaced, or provided in different shapes such as chevrons, convoluted lines, etc.
A delay unit may be configured with multiple printed timing strips connected at their starting points to a common input “bus” or to a common pick-up charge and at their discharge points to a common output “bus” or to a common relay charge. In this way the fastest burning strip always initiates the output charge. Since the distribution of actual burn times of the multiple timing strips is expected to be distributed normally, such an arrangement effectively truncates the normal distribution of burn times and decreases the standard deviation. Although the nominal burn time is also shifted in the process, this can be compensated for by adjusting the length of the strips. The result is a decrease of the standard deviation of burn times of the individual strips. The low critical diameter of printed nanoenergetic material timing strips allows a large number to be deposited on the substrate, leading to a significant improvement in timing variation performance among many mass-produced delay units of the present invention.
Referring now to
In this embodiment, the fastest burning of the linear strips 914c will set the timing of the burning from input section 914a to output section 914b.
A delay unit of the present invention which is particularly well adapted to be formed into a configuration other than a flat configuration is particularly useful as a fuze component. During the first step of fabrication of this type of delay unit, a timing strip or strips as described above is applied to a thin, flexible substrate, for example, paper, reinforced paper, Tyvek® sheet, Mylar® sheet, plastic or like material. The substrate may be rectangular in shape. Next, pick-up and relay charges are printed or otherwise applied to either end of the substrate so that they connect with or overlap the timing strip. A thin, flexible laminate composed of any suitable material, e.g., a material which is identical or similar to that of the substrate, is applied so that it covers the timing strip completely, but leaves the pick-up and relay charges exposed. The laminate can be attached to the substrate using an adhesive, mechanical means, or any suitable means. The assembly can now be rolled or otherwise formed into a suitable shape for insertion into a holder or container. For example, the laminate may be rolled into a cylinder and inserted into a standard cylindrical detonator shell. In this case, a plug, which optionally may be tapered and may be made of any suitable material, e.g., a suitable plastic, is inserted inside the detonator shell to mechanically hold it in place and to prevent the input signal to the detonator from flashing through to either the relay charge or the detonator output charge, thereby by-passing the timing strip. The assembly constitutes a delay element, as the input signal ignites the pick-up charge, burns the timing strip, and ignites the relay charge.
A tapered plug 170 may be inserted within cylindrically-rolled laminated delay unit 1010′ as described below in connection with
Tapered plug 170 is inserted within laminated delay unit 1010 for a distance sufficient to leave pick-up charge 1016a exposed. Tapered plug 170 does not interfere with the ignition of timing strip 1014 by pick-up charge 1016 because the tapered plug 170 is separated from timing strip 1014 by laminate sheet 166. Laminate sheet 166 protects timing strip 1014 both against abrasion, e.g., by tapered plug 170, and delamination from substrate 1012 during the rolling operation.
Referring now to
Generally, any one or more “adjustment structures”, i.e., jump gaps, retardants, accelerants, bridging strips or placement of pick-up and/or relay charges, may be used to adjust the burn time and therefore the delay period of the delay unit. The configuration and/or composition of the adjustment structure may either be predetermined or based on data derived from functioning the calibration strip.
While the invention has been described in detail with respect to a specific embodiment thereof, it will be appreciated that the invention has other applications and may be embodied in numerous variations of the illustrated embodiment. For example, the delay unit of the invention may be used in explosive or signal transfer devices other than detonators, and is generally usable in any device in which it is desired to interpose a time delay between explosive or energetic events.
This application claims the benefit of priority of provisional Patent Application Ser. No. 60/650,782, entitled “Delay Unit and Method of Making the Same”, filed on Feb. 8, 2005, and provisional Patent Application Ser. No. 60/713,233, entitled “Delay Unit and Method of Making the Same”, filed on Sep. 1, 2005.
Number | Name | Date | Kind |
---|---|---|---|
2436305 | Johnson | Feb 1948 | A |
3020610 | Rejdak | Feb 1962 | A |
3050409 | Bayer | Aug 1962 | A |
RE25277 | Toulmin, Jr. | Oct 1962 | E |
3089798 | Rejdak | May 1963 | A |
3118798 | Winckler | Jan 1964 | A |
3160537 | Trafton, Jr. | Dec 1964 | A |
3168090 | Billhardt | Feb 1965 | A |
3254970 | Dittrich et al. | Jun 1966 | A |
3322515 | Dittrich et al. | May 1967 | A |
3325316 | MacDonald | Jun 1967 | A |
3344210 | Silva | Sep 1967 | A |
3392015 | Badia | Jul 1968 | A |
3436248 | Dittrich et al. | Apr 1969 | A |
3489534 | Levinstein | Jan 1970 | A |
3503814 | Helms, Jr. et al. | Mar 1970 | A |
3526953 | Levinstein | Sep 1970 | A |
3560863 | Baumoel | Feb 1971 | A |
3613589 | Apstein et al. | Oct 1971 | A |
3867265 | Hansson | Feb 1975 | A |
3899306 | Knopp et al. | Aug 1975 | A |
3941058 | Gawlick et al. | Mar 1976 | A |
3989606 | Kampert | Nov 1976 | A |
4068592 | Beuchat | Jan 1978 | A |
4126522 | Edlund | Nov 1978 | A |
4239004 | Day et al. | Dec 1980 | A |
4349612 | Baldi | Sep 1982 | A |
4374686 | Davitt et al. | Feb 1983 | A |
4741811 | Lefebvre et al. | May 1988 | A |
4742773 | Bartholomew et al. | May 1988 | A |
4840820 | Schultz et al. | Jun 1989 | A |
4848646 | Morishita et al. | Jul 1989 | A |
4989515 | Kelly et al. | Feb 1991 | A |
5015340 | Colombier et al. | May 1991 | A |
5031538 | Dufrane et al. | Jul 1991 | A |
5046425 | Gibbons, Jr. et al. | Sep 1991 | A |
5401596 | Stoilov et al. | Mar 1995 | A |
5406890 | Marsh et al. | Apr 1995 | A |
5522318 | Gladden et al. | Jun 1996 | A |
5538795 | Barbee, Jr. et al. | Jul 1996 | A |
5547715 | Barbee, Jr. et al. | Aug 1996 | A |
5623117 | Lewis | Apr 1997 | A |
5721493 | Paxton | Feb 1998 | A |
5843538 | Ehrsam et al. | Dec 1998 | A |
5885321 | Higa et al. | Mar 1999 | A |
6006671 | Yunan | Dec 1999 | A |
6062143 | Grace et al. | May 2000 | A |
6110266 | Gonzalez-Blanco et al. | Aug 2000 | A |
6178623 | Kitazawa et al. | Jan 2001 | B1 |
6258461 | Baldi et al. | Jul 2001 | B1 |
6298784 | Knowlton et al. | Oct 2001 | B1 |
6491766 | Baldi et al. | Dec 2002 | B1 |
6534194 | Weihs et al. | Mar 2003 | B2 |
6640719 | Pacella et al. | Nov 2003 | B1 |
6692630 | Morin et al. | Feb 2004 | B2 |
6712917 | Gash et al. | Mar 2004 | B2 |
6736942 | Weihs et al. | May 2004 | B2 |
6780303 | Colombier et al. | Aug 2004 | B2 |
6803244 | Diener et al. | Oct 2004 | B2 |
6863992 | Weihs et al. | Mar 2005 | B2 |
7005573 | Lionetta et al. | Feb 2006 | B2 |
7026016 | Bauer | Apr 2006 | B2 |
7105740 | Allaire et al. | Sep 2006 | B2 |
7146912 | Hallin et al. | Dec 2006 | B2 |
7316186 | Robinson et al. | Jan 2008 | B1 |
20010002297 | Schweizer et al. | May 2001 | A1 |
20040031411 | Novotney et al. | Feb 2004 | A1 |
20040060625 | Barbee, Jr. et al. | Apr 2004 | A1 |
20050115449 | Kinley | Jun 2005 | A1 |
20050155752 | Larson et al. | Jul 2005 | A1 |
20050181259 | Roberge | Aug 2005 | A1 |
20060121306 | Wijenberg et al. | Jun 2006 | A1 |
20060220216 | Mizuno et al. | Oct 2006 | A1 |
Number | Date | Country |
---|---|---|
38 41 690 | Jun 1990 | DE |
0 487 472 | May 1992 | EP |
1 282 170 | Feb 2003 | EP |
2 626 875 | Aug 1989 | FR |
2 049 651 | Dec 1980 | GB |
57202045 | Dec 1982 | JP |
WO 9851749 | Nov 1998 | WO |
WO 2004011396 | Feb 2004 | WO |
WO 2004106268 | Dec 2004 | WO |
WO 2004106268 | Dec 2004 | WO |
Number | Date | Country | |
---|---|---|---|
20060236887 A1 | Oct 2006 | US |
Number | Date | Country | |
---|---|---|---|
60650782 | Feb 2005 | US | |
60713233 | Sep 2005 | US |