WO2010051395A1 - Composition de personnalisation de matière : système ia - Google Patents

Composition de personnalisation de matière : système ia Download PDF

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Publication number
WO2010051395A1
WO2010051395A1 PCT/US2009/062662 US2009062662W WO2010051395A1 WO 2010051395 A1 WO2010051395 A1 WO 2010051395A1 US 2009062662 W US2009062662 W US 2009062662W WO 2010051395 A1 WO2010051395 A1 WO 2010051395A1
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WIPO (PCT)
Prior art keywords
composition
gas
carbon
radiation
added
Prior art date
Application number
PCT/US2009/062662
Other languages
English (en)
Inventor
Christopher J. Nagel
Original Assignee
Electromagnetics Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Electromagnetics Corporation filed Critical Electromagnetics Corporation
Priority to EP09824146.6A priority Critical patent/EP2351047A4/fr
Priority to CN200980153308.7A priority patent/CN102272862B/zh
Priority to CA2742080A priority patent/CA2742080A1/fr
Publication of WO2010051395A1 publication Critical patent/WO2010051395A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/52—Manufacture of steel in electric furnaces
    • C21C5/5241—Manufacture of steel in electric furnaces in an inductively heated furnace
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/072—Treatment with gases
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0026—Pyrometallurgy
    • C22B15/006—Pyrometallurgy working up of molten copper, e.g. refining
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/16—Remelting metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Definitions

  • the present invention relates to the unexpected discovery that the addition of carbon is not essential to tailoring materials.
  • the discovery was made as a result of an experiment of the previously described process where the induction furnace failed to bring the material up to the targeted initial temperature and prior to the planned addition of carbon. It was then appreciated that tailoring can be achieved even in the absence of carbon addition, resulting in products that are "essentially carbon free.” This serendipitous discovery gave rise to the inventions described and claimed herein.
  • the materials that can be tailored in accordance with the present invention include matter comprised of 'p', 'd', and/or T atomic orbitals and include but are not limited to metals.
  • the tailored materials produced in accordance with the invention are defined by, can be distinguished and/or are characterized by a change in one or more energy, electronic properties, physical properties, and the like.
  • X-ray fluorescence spectroscopy is one method of detecting and distinguishing tailored materials. Changes in properties can be made and/or controlled to be transient, fixed, or adjustable (temporarily permanent) and include properties such as mechanical, electrical, chemical, thermal, engineering, and physical properties, as well structural character of the composition of matter (e.g., alignment, orientation, order, anisotropy, and the like).
  • the present invention includes manufactured metals and alloys that are essentially carbon-free and are characterized by the x-ray fluorescence spectrometry plots and elemental abundance tables (obtained from x-ray fluorescence analysis) such as those described
  • the present invention relates to a method of processing, or tailoring, a material, such as a metal or an alloy of metals, the improvement comprising tailoring in the absence of carbon.
  • the method generally requires subjecting a material to a symmetrically or asymmetrically oscillating electromagnetic field in the absence of a step of adding carbon. This method can be achieved by subjecting the material to an iterative cycling between two or more temperatures (which can be a consequence of the oscillating field).
  • the method comprises the steps of:
  • step (C) optionally repeating step (B) at the same or different temperatures, one of said temperatures is preferably greater than at least one or both of the temperatures of step (B); and (D) optionally, cooling the material obtained from step (B) or (C) and selecting a tailored material.
  • the incremental increasing can be, for example, where the molten material is raised and decreased between two set temperatures (Tl and T2). Alternatively, the temperatures of each cycle can be changed (increased or decreased).
  • the method of the invention can also include an optional holding step whereby the material is held at a selected temperature for a selected period of time, optionally in the presence of gas addition.
  • the processes of the invention further comprise at least one (e.g., any 2, 3, 4, 5, 6, 7, 8 or 9) of the following steps:
  • the gas or gaseous addition e.g., nitrogen, hydrogen, and/or noble gas
  • the gas or gaseous addition is added to the material through a lance set at a level above the liquid level;
  • at least one of the gases or gaseous additions comprises a gas mixture;
  • the present invention is a method of processing copper, or other metal or alloy comprising subjecting copper, or other material, metal or alloy to an iterative energy cycling process in the absence of carbon under conditions suitable to achieve tailoring and testing the product of the process for tailoring and selecting a tailored copper.
  • the oscillating magnetic field can be achieved by delivering energy in a form other than heat, as described in more detail below.
  • Advantages of the present invention include a method of processing metals into new compositions of matter and producing and characterizing compositions of matter with altered physical and/or electrical properties without the need to add a carbon source.
  • FIGS 1 A-IH illustrate the furnace power cycling and bath temperature during the experiment.
  • the present invention relates to new compositions of matter, referred to herein as "manufactured” materials, metals or alloys of metals.
  • a “manufactured” metal or alloy is a metal or alloy which exhibits a change in electronic structure, such as that seen in a fluid XRF spectrum.
  • the American Heritage College Dictionary, Third Edition defines "fluid” as changing or tending to change.
  • Metals of the present invention are generally p, d, or f block metals.
  • Metals include transition metals such as Group 3 metals (e.g., scandium, yttrium, lanthanum), Group 4 metals (e.g., titanium, zirconium, hafnium), Group 5 metals (vanadium, niobium, tantalum), Group 6 metals (e.g., chromium, molybdenum, tungsten), Group 7 metals (e.g., manganese, technetium, rhenium), Group 8 metals (e.g., iron, ruthenium, osmium), Group 9 metals (e.g., cobalt, rhodium, iridium), Group 10 metals (nickel, palladium, platinum), Group 11 metals (e.g., copper, silver, gold), and Group 12 metals (e.g., zinc, cadmium, mercury).
  • Group 3 metals e.g.,
  • Metals of the present invention also include alkali metals (e.g., lithium, sodium, potassium, rubidium, and cesium) and alkaline earth metals (e.g., beryllium, magnesium, calcium, strontium, barium). Additional metals include lanthanides, aluminum, gallium, indium, tin, lead, boron, germanium, arsenic, antimony, tellurium, bismuth, thallium, polonium, astatine, and silicon.
  • the present invention also includes alloys of metals. Alloys are typically mixtures of metals. Alloys of the present invention can be formed, for example, by melting together two or more of the metals listed above.
  • Preferred alloys include those comprised of copper, gold, and silver; tin, zinc, and lead; tin, sodium, magnesium, and potassium; iron, vanadium, chromium, and manganese; nickel, tantalum, hafnium, and tungsten; copper and ruthenium; nickel and ruthenium; cobalt and ruthenium; cobalt, vanadium and ruthenium; and nickel, vanadium and ruthenium. Materials other than metals can also be tailored in accordance to the invention.
  • the present invention also includes alloys of metals or mixtures of other materials. Alloys are typically mixtures of metals. Alloys of the present invention can be formed, for example, by melting together two or more of the metals listed above.
  • a cycle of the present invention includes a period of time where the temperature of the material is varied between two distinct temperatures (Tl to T2, wherein T1 ⁇ T2). Over a period of time, a cycle involves varying the temperature including a period of raising (or increasing) the temperature of the material and a period when the temperature decreases (either passively, such as by heat transfer to the surrounding environment, or actively, such as by mechanical means), in any order. Inert gas can be added during the entire cycle or part of the cycle.
  • the temperatures selected for each cycle is preferably increased such that Tl of cycle 2 is greater than Tl of cycle 1 and T2 of cycle 2 is greater than T2 of cycle 1, and so on.
  • Each cycle between to two temperatures, Tl and T2 can include two or more iterations.
  • An iterative cycle process is a process comprising two or more cycles, whereby one or more of the cycles are carried out between two or more temperatures.
  • the induction furnace was set to bring the temperature of the reactor up to 2462 0 F at a rate to not exceed 150°F/hr, controlled by a feedback loop. Because of insufficient insulation wrapping, the temperature in the induction furnace entered into an iterative cycling heating process that reached a final temperature of 2386 0 F. The material subjected to the process unexpectedly was tailored.
  • cycles of the present invention can vary in duration and can be symmetric or asymmetric.
  • the period of increasing the metal or alloy temperature is equal to the period of decreasing the metal or alloy temperature.
  • the period of increasing the metal or alloy temperature is different than the period of decreasing the metal or alloy temperature.
  • the period of increasing the metal or alloy temperature can be longer than or shorter than the period of decreasing the metal or alloy temperature.
  • the time period is, in part, dictated by the rate of heating and cooling which is practical by the equipment (e.g., induction furnace) used, the material selected and the mass of material being processed.
  • the time period of each sweep of an iteration or cycle can be selected to produce sets of energy patterns.
  • a cycle can also include, or be interrupted or ended with, a holding step.
  • the material can be held at an energy level (as measured, for example, by the temperature or degree of carbon saturation) for a selected period of time.
  • the holding period can be several minutes to several hours or more.
  • the material can be held for 60 minutes or 5 minutes. More than one hold step can be incorporated into the process and can be included in an iteration of steps.
  • the number of cycles in a step is generally an integer or half-integer value.
  • the number of cycles in a step can be one or more, one to forty, or one to twenty.
  • the number of cycles can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40.
  • the number of cycles in a step can be 0.5, 1.5, 2.5, 3.5, 4.5, 5.5, 6.5, 7.5, 8.5, 9.5, 10.5, 11.5, 12.5, 13.5, 14.5, 15.5, 16.5, 17.5, 18.5, 19.5, 20.5, 21.5, 22.5, 23.5, 24.5, 25.5, 26.5, 27.5, 28.5, 29.5, or 30.5.
  • a step comprising a half-integer or a non-integer quantity of cycles either heating or cooling can occur first.
  • the process is preferably conducted in a molten state.
  • Cycling temperatures for tailoring molten metals can be typically between about 900 0 F to about 3000 0 F.
  • the temperature can be about 1932 0 F to about 2467 0 F for copper; about 2368 0 F to about 2855 0 F for nickel; about 2358 0 F to about 2805 0 F for cobalt; and so on.
  • Gas such as nitrogen, hydrogen or a noble gas
  • the gas provides a third body effect for the reaction facilitating energy exchange.
  • hydrogen, helium, nitrogen, neon, argon, krypton, xenon and carbon monoxide can be added.
  • the gas is added as a mixture.
  • a preferred mixture comprises argon, helium, neon and/or krypton.
  • at least 50%, more preferably at least 80% such as at least 90% by volume argon, helium or hydrogen is present in the mixture.
  • Particularly preferred mixtures include (1) 93% argon, 5% helium and 2% neon; (2) 92% argon, 5% helium and 3% neon; (3) 95% argon and 5% helium or neon; (4) 95% helium and 5% krypton; (5) 95% nitrogen and 5% helium; (6) 97% helium and 3% neon (optionally trace amounts of krypton); (7) 97% argon and 3% neon; (8) 60% argon and 40% helium (optionally trace amounts of neon, hydrogen and/or krypton); (9) 49.5% hydrogen, 49.5% helium and 1% neon.
  • the gas can be added at various rates.
  • the gas is added in terms of the resulting agitation on the material and exchange with the material.
  • the gas can be added at a low rate, resulting in low agitation/exchange; at a modest, moderate or high or vigorous rate.
  • the gases can be mixed prior to adding or added individually. Using conventional fluid dynamic scaling models and assuming a crucible size of 3.75 inches LD.
  • examples of low agitation can be achieved by adding about 0.25 SLPM; modest agitation can be achieved by adding between about 1.25 SLPM; moderate agitation can be achieved by adding between about 2.5 SLPM and high agitation can be achieved agitation by adding between about 5.0 SLPM.
  • Selecting low agitation generally results in clearly defined bubbles in a quiescent bath.
  • High agitation generally results in a turbulent well-mixed bath. Modest and moderate agitation rates enables mixing and exchange to be adjusted between these extremes.
  • the rate of addition can begin at one level and be changed during the step to a different level (e.g., from a low rate to a vigorous rate).
  • Flow rates for a crucible size of 8.875 inches, with a 16.5 inch height, holding 100 lbs of copper can be determined using standard scaling techniques based on bubble size and residence time distributions to achieve similar transport phenomena.
  • the gas can be added to the material either below or above (including across) the surface level of the material.
  • the gas When the gas is added below the surface level, it can be added via injection ports from the bottom or sides of the reactor. However, it is often preferred to add the gas via a lance.
  • the lance can be positioned to provide gas entry below the surface level, e.g. at the bottom of the reactor, midpoint or near the surface of the material.
  • the lance can be placed to direct the gas across the surface of the material or toward at the surface.
  • the gas can be directed at a force that creates an indentation in the surface.
  • the lance can be placed along the centerline of the reactor. However, it is often desirable to place the lance off center, e.g., at about two thirds radius point as measured from the center. Lance placement involves consideration of mass/energy transfer, interaction of multiple lances, and physicochemical and photochemical characteristics of the reactants being added.
  • the material can be subjected or exposed to the gas either during the entire process or a cycle or series of cycles or alternating cycles, during the cooling step or thereafter as a post treatment step.
  • the gas is exposed to radiation.
  • the exposure can be applied in a continuous or batch mode.
  • the radiation source can be applied as the gas moves through a conduit for the gas source to the reactor.
  • the conduit is preferably not opaque and is more preferably translucent or transparent.
  • the radiation can be applied in an open or closed system.
  • a closed system entails exposing the gas to the specified radiation in the substantial absence of other radiation sources (e.g., visible light, magnetic fields above background). This can be easily accomplished by building a black box surrounding a segment of the conduit and placing the radiation source(s) within the black box.
  • An open system can also be employed where the radiation source(s) are not shielded from ambient light.
  • the material itself can be subjected to radiation (an additional form of applying an oscillating electromagnetic field), either in lieu of, during or after the processes described herein.
  • a tailored metal can be subjected to radiation to further modify the properties of the metal.
  • the radiation sources can be selected to provide a broad range of emitted wavelengths.
  • the radiation can range from infrared to ultraviolet wavelengths.
  • examples of preferred radiation sources emit into the range of 160 nm to 1000 nm; in another embodiment, examples of preferred radiation sources emit and into the range of 180 nm to 1100 nm; and in a more preferred embodiment examples of preferred radiation sources emit into the range of 400 nm to 700 nm.
  • the radiation can be conveniently supplied by short arc lamps, high intensity discharge lamps, pencil lamps, lasers, light emitting diodes, incandescent, fluorescent, and/or halogens for example.
  • suitable high intensity discharge lamps include mercury vapor, sodium vapor and/or metal halide.
  • Short arc lamps include mercury, xenon or mercury-xenon lamps.
  • Pencil lamps include neon, argon, krypton, xenon, short wave ultraviolet, long wave ultraviolet, mercury, mercury/argon, mercury/neon, and the like.
  • the radiation can also include (or exclude), incandescent or fluorescent light and/or natural sources of light, such as electromagnetic radiation emitted by celestial bodies.
  • the radiation sources can optionally be used in combination with light shields or wavelength filters.
  • UVP Pen-Ray Filters include the G-275 filter which absorbs visible light while transmitting ultraviolet at 254 nm and the G-278 filter which converts shortwave radiation to longwave radiation at 365 nm.
  • Pen-Ray Shields include Shield A which has a 0.04 inch ID hole for point-like source, Shield B which has a 0.31 x 0.63 inch window, and Shield C which has a 0.19 x 1.5 inch window. Filters and shields can also be obtained from Newport Corp. (Irvine, CA).
  • the Newport 6041 Short Wave Filter absorbs visible lines; the 6042 Long Wave Conversion Filter attenuates the 253.7nm Hg line and fluoresces from 300-400 nm; and the 6057 Glass Safety Filter absorbs the 253.7 nm Hg line and attenuates the 312.6 nm line.
  • the Aperture Shields offered by Newport include the 6038 Pinhole Shield which has a 0.040 inch (lmm) diameter, the 6039 Small Aperture Shield which has a 0.313 x 0.375 inch window and the 6040 Large Aperture Shield with a 0.188 x 1.50 inch window. Filters and shields can also be obtained from Edmund Industrial Optics Inc. (Barrington, NJ).
  • the Edmund UV Light Shield A has a lmm inner diameter drilled hole; Shield B has a 7.9mm x 15.9mm aperture; and Shield C has a 4.8 mm x 38.2 mm aperture.
  • the orientation of the lamp can also impact upon the result obtained.
  • the radiation source can be fixed to direct the radiation directly towards, perpendicular, away or parallel to the conduit directing the gas, or its entry or exit point.
  • the gases can be those discussed above or other gases, such as air or oxygen.
  • the radiation source can be positioned horizontally, vertically and/or at an angle above, below across from the conduit.
  • the base of a pencil lamp (or other radiation source) can be set at the same height of the conduit and the tip of the lamp directed or pointed toward the conduit.
  • the base of the pencil lamp (or other radiation source) can be set at the height of the conduit and the lamp directed at a 30° (40°, 45°, 50°, 55°, 60°, or 90°) angle above (below) the conduit.
  • the base of the pencil lamp can be fixed above or below the level of the conduit.
  • the tip of the pencil lamp can be pointed up or down, in the direction of the gas flow or against the gas flow or at another angle with respect to any of the above.
  • more than one of the same or different pencil lamps alone or in combination with other radiation sources can be used, set at the same or different heights, orientations and angles.
  • the lamps can be presented in alternative orders (first xenon, then mercury or vice versa).
  • the radiation source can be fixed to direct the radiation directly towards, perpendicular, away or parallel to the material.
  • the radiation source can be positioned horizontally, vertically and/or at an angle above, below across from the material.
  • the base of a pencil lamp (or other radiation source) can be set at the same height of the material and the tip of the lamp directed or pointed toward the material.
  • the base of the pencil lamp (or other radiation source) can be set at the height of the material and the lamp directed at a 30° (40°, 45°, 50°, 55°, 60°, or 90°) angle above (below) the material.
  • the base of the pencil lamp can be fixed above or below the level of the material.
  • the tip of the pencil lamp can be pointed up or down, in the direction of the gas flow or against the gas flow or at another angle with respect to any of the above.
  • more than one of the same or different pencil lamps alone or in combination with other radiation sources can be used, set at the same or different heights, orientations and angles.
  • the radiation source is a high intensity discharge lamp positioned to direct the radiation towards the material.
  • the high intensity discharge lamp is combined with one or more pencil lamps positioned proximal to the high intensity discharge lamp.
  • high intensity discharge lamps are equipped with a hood or reflector to direct the radiation.
  • one or more pencil lamps can be placed inside and/or behind the reflector.
  • the distance between the radiation source and the material and/or gas conduit can impact the results achieved.
  • the lamps can be placed between about 5 and 100 cm or more from the conduit and/or material.
  • the distance between the radiation source and the material and/or gas conduit can be between about 100 cm and 5 meters or more.
  • the radiation can be filtered.
  • Filters such as colored glass filters, available from photography supply shops, for example, can be used.
  • the filter can be other materials, such as water, gas (air or other gas), a manufactured or tailored material, such as those materials described or made herein, or a material of selected density, chemical make-up, properties or structure.
  • the filter can be placed between the radiation source(s) and the target metal or alloy or gas used in the method. Filters can also be called "forcing functions.” Forcing functions can be used in conjunction with electromagnetic radiation sources to induce or affect a change in a material.
  • gases may be injected into apparatus containing a forcing function to modify the performance of the assembly.
  • the radiation source has an environment which is different from that of the material. This can be accomplished by directing a gas flow into the lamp environment. Where the radiation source is a pencil lamp within a box to radiate a gas, this can be accomplished by direct gas flow into the box. In other embodiments, the radiation source can be a short arc lamp or a short arc lamp assembly. In such embodiments, the gas can be introduced into the reflector proximate to the lamp. The gas includes those gases discussed above.
  • the radiation can be applied continuously or discontinuously (e.g. pulsed or toggled) and its intensity can be modulated. Where the radiation is applied continuously, the radiation can begin prior to introduction of the gas into the conduit or after. It can be applied for the duration of a cycle or series of cycles. Where the radiation is pulsed, the length of each pulse can be the same or different. Generally, the radiation is applied to induce change, altering the gas or target materials prior to their introduction into the reactor. This is conveniently accomplished by controlling the lamps with a computer.
  • the factors to be considered in radiation source placement, exposure and sequence include the desired wavelength, intensity, and energy characteristics, the angle of incidence, and the harmonic profile to be injected into the targeted material (e.g. gas, metal, tailored metal, radiated gas and the like).
  • the radiation source and/or pencil lamp(s) and/or filters and/or target material or gas are advantageously cooled.
  • a high intensity discharge lamp is used in combination with a pencil lamp(s)
  • a short arc lamp is used in combination with pencil lamps and/or glass filters it may be advantageous to cool the pencil lamps to prevent damage as well as the glass filter to prevent breakage.
  • DC current can be applied continuously or the amperage varied, for example between 0-300 amps, such as 0-150 amps.
  • AC current can be applied continuously or varied, e.g., in a wave pattern, such as a sinusoidal wave, square wave, or triangle wave pattern of a selected frequency and amplitude.
  • 10 volts, peak to peak is used at 0-3.5 MHz, 0-28 MHz, or 0-50 MHz.
  • the peak to peak voltage was less that about 15 vdc, 10 vdc, 8 vdc, 7.2 vdc, 5 vdc, 1.7 vdc, and 1 vdc.
  • a frequency generator can be used.
  • electrodes can be placed in the reactor, such as below the surface of the material, and current applied. As with the radiation discussed above, the current can be applied to coincide with a cycle or series of cycles or during all or a part of a single step of the process. Often the power supply is turned on prior to attachment to the electrodes to avoid any power surge impacts.
  • Methods of the present invention are carried out in a suitable reactor.
  • Suitable reactors are selected depending on the amount of metal or alloy to be processed, mode of heating, extent of heating (temperature) required, and the like.
  • a preferred reactor in the present method is an induction furnace reactor, which is capable of operating in a frequency range of 0 kHz to about 10,000 kHz, 0 kHz to about 3,000 kHz, or 0 kHz to about 1,000 kHz.
  • Reactors operating at lower frequencies are desirable for larger metal charges, such that a reactor operating at 0- 3,000 kHz is generally suitable for 20 pound metal charges and a reactor operating at 0-1,000 kHz is generally suitable for 5000 pound metal charges.
  • reactors of the present method are lined with a suitable crucible.
  • Crucibles are selected, in part, based on the amount of metal or alloy to be heated and the temperature of the method.
  • Crucibles selected for the present method typically have a capacity from about five pounds to about five tons.
  • One preferred crucible is comprised of 89.07% Al 2 O 3 , 10.37% SiO 2 , 0.16% TiO 2 , 0.15% Fe 2 O 3 , 0.03% CaO, 0.01% MgO, 0.02% Na 2 O 3 , and 0.02% K 2 O, and has a 9" outside diameter, a 7.75" inside diameter, and a 14" depth.
  • a second preferred crucible is comprised of 99.68% Al 2 O 3 , 0.07% SiO 2 , 0.08% Fe 2 O 3 , 0.04% CaO, and 0.12% Na 2 O 3 , and has a 4.5" outside diameter, a 3.75" inside diameter and a 10" depth.
  • the cooling step can alter the results of the process. Such cooling can include gradual and/or rapid cooling steps. Gradual cooling typically includes cooling due to heat exchange with air or other gas over 1 to 72 hours, 2 to 50 hours, 3 to 30 hours, or 8 to 72 hours.
  • Rapid cooling typically includes an initial cooling with air or other gas to below the solidus temperature, thereby forming a solid mass, and placing the solid mass into a bath comprising a suitable fluid such as tap water, distilled water, deionized water, other forms of water, gases (as defined above), liquid nitrogen or other suitable liquified gases, a thermally-stable oil (e.g., silicone oil) or organic coolant, and combinations thereof.
  • the bath should contain a suitable quantity of liquid at a suitable temperature, such that the desired amount of cooling occurs.
  • the ingot can be removed from the crucible before or after completing the cooling. While the material is cooling, the environment can be stirred, mixed or agitated. This can be accomplished by maintaining a flow of coolant over the material, or agitating the cooling bath or environment. Alternatively, the coolant is not disturbed or agitated and circulation of the coolant is minimized.
  • the material is cooled in a different vessel (cooling or quench chamber).
  • the cooling chamber can be, for example, a polyethylene (or other plastic) container.
  • the ingot can be placed directly, or indirectly, into the cooling vessel (e.g., in a vertical or horizontal orientation). Generally, the ingot can be placed at least about 6 inches from the inside wall of the container. The height of the coolant can be at least about 12 inches above and below the surface of the ingot.
  • a refractory material e.g., a ceramic block rinsed with coolant (e.g., DI water) and, optionally dried or allowed to dry
  • coolant e.g., DI water
  • the material can be removed, manually or robotically, to a clean, protected surface.
  • This removal may be accomplished manually using a pair of tongs (e.g. cast iron, steel, stainless steel, nickel, titanium, tungsten or other high temperature melting transition metal).
  • Manual removal can also be accomplished by donning heavy, insulated, heat resistant gloves.
  • the crucible should be removed before or after cooling.
  • the crucible can be removed by gently peeling it away from the material.
  • a hammer, ram or wedge can be used to perform this function.
  • care should be used to avoid striking the material hard with the hammer or otherwise causing a substantial impact upon or metal contact with the material.
  • the crucible removal can be performed in the presence of air at about 350 ⁇ 75°F, 750 ⁇ 250°F, 1100 ⁇ 250°F, or at T S ohdus -75 0 F, Tsoiidus -5 0 F.
  • a new composition of matter of the present invention can manifest itself as a transient, adjustable, or permanent change in energy and/or associated properties, as broadly defined.
  • Property change can be exhibited as or comprise a change in: (1) structural atomic character (e.g., XES/XRF peak creation, peak fluidity, peak intensity, peak centroid, peak profile or shape as a function of material/sample orientation, atomic energy level(s), and TEM, STM, MFM scans); (2) electronic character (e.g., SQUID, scanning SQUID, scanning magnetoresistive microscopy, scanning magnetic microscope, magnetometer, non-contact MFM, electron electromagnetic interactions, quantum (or topological) order 1 ' 2 , quantum entanglement 3 , Jahn-Teller effect, ground state effects, electromagnetic field position/orientation, energy gradients, Hall effect, voltage, capacitance, voltage decay rate, voltage gradient, voltage signature including slope of decay and/or change of slope decay, voltage magnitude, voltage orientation); (3) structural molecular or atomic character (e.g
  • X-ray fluorescence spectrometry is described in "X-Ray Fluorescence Spectrometry", by George J. Havrilla in “Handbook of Instrumental Techniques for Analytical Chemistry," Frank A. Settle, Ed., Prentice-Hall, Inc: 1997, which is incorporated herein by reference.
  • XRF spectrometry is a well-known and long-practiced method, which has been used to detect and quantify or semi-quantify the elemental composition (for elements with Z > 11) of solid and liquid samples. This technique benefits from minimal sample preparation, wide dynamic range, and being nondestructive.
  • XRF data are not dependent on which dimension (e.g., axial or radial) of a sample was analyzed. Accuracy of less than 1% error can generally be achieved with XRF spectrometry, and the technique can have detection limits of parts per million.
  • XRF spectrometry first involves exciting an atom, such that an inner shell electron is ejected. Upon ejection of an electron, an outer shell electron will "drop" down into the lower-energy position of the ejected inner shell electron. When the outer shell electron "drops" into the lower-energy inner shell, x-ray energy is released. Typically, an electron is ejected from the K, L, or M shell and is replaced by an electron from the L, M, or N shell.
  • each element in the Periodic Table has a standard pattern of x-ray emissions after being excited by a sufficiently energetic source, since each such element has its own characteristic electronic state.
  • a pattern of emitted x-ray energies to values found in tables, such as those on pages 10-233 to 10-271 of "Handbook of Chemistry and Physics, 73 rd Edition," edited by D. R. Lide, CRC Press, 1992, which is incorporated herein by reference, one can identify which elements are present in a sample.
  • the intensity of the emitted x-rays allows one to quantify the amount of an element in a sample.
  • the XRF technique uses a detector such as a Si(Li) detector, capable of simultaneously measuring the energy and intensity of x-ray photons from an array of elements.
  • EDXRF is well-suited for rapid acquisition of data to determine gross elemental composition.
  • the detection limits for EDXRF are in the range of tens to hundreds of parts-per-million.
  • a wavelength- dispersive technique (WDXRF) is generally better-suited for analyses requiring high accuracy and precision.
  • WDXRF uses a crystal to disperse emitted x-rays, based on Bragg' s Law.
  • Natural crystals such as lithium fluoride and germanium, are commonly used for high-energy (short wavelength) x-rays, while synthetic crystals are commonly used for low-energy (longer wavelength) x-rays. Crystals are chosen, in part, to achieve desired resolution, so that x-rays of different energies are dispersed to distinguishable 2 ⁇ angles.
  • WDXRF can either measure x-rays sequentially, such that a WDXRF instrument will step through a range of 2 ⁇ angles in recording a spectrum, or there will be detectors positioned at multiple 2 ⁇ angles, allowing for more rapid analysis of a sample. Detectors for WDXRF commonly include gas ionization and scintillation detectors.
  • Results from EDXRF and results from WDXRF can be compared by determining the relationship between a 2 ⁇ angle and the wavelength of the corresponding x-ray (e.g., using Bragg's Law) and converting the wavelength into energy (e.g., energy equals the reciprocal of the wavelength multiplied by Planck's constant and the velocity of light).
  • Analysis of emitted x-rays can be carried out automatically or semi- automatically, such as by using a software package (e.g., UniQuant® software, Thermo Fisher Scientific, Inc.) for either EDXRF or WDXRF.
  • UniQuant® is used for standard-less, semi-quantitative to quantitative XRF analysis using the intensities measured by a sequential x-ray spectrometer.
  • the software package unifies all types of samples into one analytical program.
  • the UniQuant® software program is highly effective for analyzing samples for which no standards are available. Sample preparation is usually minimal or not required at all. Samples can be of very different natures, sizes and shapes.
  • Elements from fluorine or sodium up to uranium, or their oxide compounds can be analyzed in samples such as a piece of glass, a screw, metal drillings, lubricating oil, loose fly ash powder, polymers, phosphoric acid, thin layers on a substrate, soil, paint, the year rings of trees, and, in general, those samples for which no standards are available.
  • the reporting is in weight % along with an estimated error for each element.
  • an XRF spectrum is composed of data channels.
  • Each data channel corresponds to an energy range and contains information about the number of x-rays emitted at that energy.
  • the data channels can be combined into one coherent plot to show the number or intensity of emitted x-rays versus energy or 2 ⁇ angle (the 2 ⁇ angle is related to the wavelength of an x- ray), such that the plot will show a series of peaks.
  • An analysis of the peaks by one skilled in the art or the software package can identify the correspondence between the experimentally-determined peaks and the previously-determined peaks of individual elements.
  • peak location i.e., the centroid of the peak with respect to energy or 2 ⁇ angle
  • peak profile/ shape i.e., the centroid of the peak with respect to energy or 2 ⁇ angle
  • peak creation i.e., the centroid of the peak with respect to energy or 2 ⁇ angle
  • a typical software package is programmed to correlate certain data channels with the emitted x-rays of elements. Quantification of the intensity of emitted x-rays is accomplished by integrating the XRF spectrum over a number of data channels. Based on the measured intensities and the previously-compiled data on elements, the software package will integrate over all data channels, correlate the emitted x-ray intensities, and will then calculate the relative abundance or quantity of elements which appear to be present in a sample, based upon comparison to the standards.
  • Composition of matter changes produced by the present invention will generally be characterized by an XRF spectrum that reports: (1) the presence of an element which was not present in the starting material and was not added during the process; (2) an increased amount of an element that was not added to the process in the amount measured; or, (3) a decreased amount of an element that was not removed during the process in the amount indicated. Examples of (3) include a reduction in identifiable spectra referencing the sum before normalization and/or reappearance of an element upon combustion. Products of the present invention can also be characterized by the difference between XRF Uniquant analysis such as by burning the sample (e.g., LECO analysis), described in more detail below.
  • a "LECO” analysis is meant to include an analysis conducted by the CS-300 Carbon/Sulfur determinator supplied by a LECO computer.
  • the CS-300 Carbon/Sulfur determinator is a microprocessor based, software driven instrument for measurement of carbon and sulfur content in metals, ores, ceramics and other inorganic materials.
  • Analysis begins by weighing out a sample (I g nominal) into a ceramic crucible on a balance. Accelerator material is added, the crucible is placed on the loading pedestal, and the ANALYZE key is pressed. Furnace closure is performed automatically, then the combustion chamber is purged with oxygen to drive off residual atmospheric gases. After purging, oxygen flow through the system is restored and the induction furnace is turned on. The inductive elements of the sample and accelerator couple with the high frequency field of the furnace. The pure oxygen environment and the heat generated by this coupling cause the sample to combust. During combustion all elements of the sample oxidize. Carbon bearing elements are reduced, releasing the carbon, which immediately binds with the oxygen to form CO and CO2, the majority being CO2. Also, sulfur bearing elements are reduced, releasing sulfur, which binds with oxygen to form SO 2 .
  • Sample gases are swept in the carrier stream.
  • Sulfur is measured as sulfur dioxide in the first IR cell.
  • a small amount of carbon monoxide is converted to carbon dioxide in the catalytic heater assembly while sulfur trioxide is removed from the system in a cellulose filter.
  • Carbon is measured as carbon dioxide in the IR cells, as gases flow trough the IR cells.
  • the relative abundances will total 100% prior to normalization. However, for a variety of reasons, such as improper or insufficient calibration, and/or non-planar sample surface the relative abundances will not total 100% prior to normalization. Another reason that the relative abundances of elements do not total 100% prior to normalization is that a portion of the XRF spectrum falls outside of the data channels that the software package correlates with an element (i.e., a portion of the XRF spectrum is not recognized as belonging to an element and is not included in the relative abundance calculation). In this case, the relative abundances will likely total less than 100% prior to normalization. Further, the samples will often have anisotropic characteristics whereby an axial scan is distinct from a radial scan.
  • products of the invention may be characterized by an XRF spectrum that is not recognized by the Uniquant software (e.g., sum of known concentrations before normalization is less than 100%) described herein in an amount, for example, of less than 98%, such as less than 90%, such as less than 80%.
  • the software package reports or detects one or more elements not detected by other methods or are detected in different quantities.
  • X-ray emission spectrometry a technique analogous to XRF, also provides electronic information about elements.
  • XES X-ray emission spectrometry
  • a lower-energy source is used to eject electrons from a sample, such that only the surface (to several micrometers) of the sample is analyzed.
  • a series of peaks is generated, which corresponds to outer shell electrons replacing ejected inner shell electrons.
  • the peak shape, peak fluidity, peak creation, peak intensity, peak centroid, and peak profile are expected to be essentially the same, within experimental error and matrix effects, for two samples having the same composition.
  • XES analysis of the control standard compared to the atomically altered (i.e., manufactured or tailored) state can also be analyzed.
  • Manufactured copper in the axial direction exhibits similar composition to natural copper (i.e., 99.98%wt), but radial scans exhibit new peaks in the region close to naturally occurring S, Cl, and K.
  • the shifting centroid of the observed peaks from the natural species i.e., S, Cl, and K
  • Conventional chemical analysis performed using a LECO (IR) analyzer to detect SO x in the vapor phase post sample combustion confirmed the absence of sulfur at XES lower detection limits.
  • Non-contact, magnetic force microscopy image or scanning tunneling microscopy (STM) scan can also confirm the production of a new composition of matter or manufactured or tailored material, identified by an altered and aligned electromagnetic network. Individually, and from differing vantage points, these scans show the outline of the changed electromagnetic energy network.
  • New compositions of matter can be electronically modified to induce long range ordering/alignment.
  • Optical microscopy and SEM imaging of the material verifies the degree and extent of long range ordering achieved.
  • Non-contact, magnetic force microscopy image or scanning tunneling microscopy (STM) scans can also confirm the production of a new composition of matter or manufactured or tailored material, identified by an altered and aligned electromagnetic network. Individually, and from differing vantage points, these scans can show the outline of the changed electromagnetic energy network.
  • Non- contact MFM imaging can show that products of the invention often possess clear pattern repetition and intensity of the manufactured material when compared to the natural material, or starting material.
  • Products of the invention can be characterized by the presence of magnetic properties in high purity, non-magnetic metals, such as elemental copper (e.g., 99.98 %wt)- Products can also be characterized by color changes.
  • the variation in color of copper products ranged from black, copper, gold, silver and red. Other visual variations included trans lucency and near transparency at regions. While not being bound by theory, the alteration of the metal's electronic state along the continuum enables the new composition of matter's color to be adjusted along the continuum.
  • Other products of the processes are characterized by changes in hardness.
  • the variation in diamond pyramid hardness between different manufactured copper samples ranged from about 25 to 90 (or 3 to 9 times higher than natural copper). Hardness change can be anisotropic.
  • Manipulation of the electrodynamic components affecting the orientation of a manufactured metal's or alloy's electromagnetic field can enable the observance of a Hall voltage (V H ).
  • Manipulation of the electrodynamic components enables intensification of electromagnetic field affording charge concentration on the surface of the atoms within the bulk as opposed to the bulk surface of the bath.
  • Properties that reflect field repositioning can include changing capacitance and voltage decay rate and voltage gradients within a conducting bulk media.
  • the products produced by the process have utilities readily apparent to those skilled in the art. Indeed, materials which comprise metals can be used to manufacture products having adjustable chemical properties (e.g., regioselectivity, regiospecificity, or reaction rate), electronic properties (e.g., band gap, susceptibility, resistivity, or magnetism), mechanical properties (e.g., ductility or hardness) and/or optical properties (e.g., color).
  • the products of this invention are essentially carbon free.
  • the products as described in US Patent 7,238,297, for example are characterized by carbon at saturation levels or above. "Essentially free of carbon", as defined in this case, means that the product has no more than the amount of carbon present in the starting material.
  • the prior art products generally contained carbon in amounts that equal or exceed saturation.
  • carbon saturation is between approximately 0.22 and 0.71 atomic%.
  • carbon saturation is about 0.04 atomic %.
  • the products of the invention are characterized by one or more electronic and/or physical characteristics described above in addition to having a carbon percentage less than saturation.
  • the product has no more than the carbon content of the material added to the process.
  • the product is essentially free of carbon and, in one embodiment, contains no detectable carbon.
  • analysis of the composition by X-ray fluorescence is a convenient method for detecting tailoring of a material. Tailoring is detected if the report generated detects the presence of an element that (1) was not present in the starting material and was not added or (2) was present in the starting material and (a) additional elements was not added or (b) was not removed or diluted.
  • the invention relates to compositions, essentially free of carbon, wherein the composition (e.g., a metal, such as copper) comprises a material characterized by an X-ray fluorescence analysis report wherein the report recites the presence of an element in the periodic table wherein said composition has not been in contact with said element; or comprises a material characterized by an X-ray fluorescence analysis report wherein the report recites a concentration of an element in the periodic table that exceeds the concentration of said element added to the composition; or comprises a material characterized by an X-ray fluorescence analysis report wherein the report recites a concentration of an element in the periodic table that is less than the concentration of said element added to the composition.
  • the composition e.g., a metal, such as copper
  • the composition e.g., a metal, such as copper
  • the composition e.g., a metal, such as copper
  • the composition e.g., a metal, such as copper
  • the composition e.g., a metal,
  • EXAMPLE 1 The object of this run was to duplicate a previously "failed run.” The prior run "failed” due to insufficient insulating wraps around the crucible causing a large heat loss an inability to reach the initial saturation temperature of 2462° F even after allowing the unit to apply maximum power - 40 Kw for three hours. After maintaining full power for 3 hours the final temperature reached on run RO 14-02- 005 was 2300° F. To duplicate, all insulating wraps were removed from the outside of the crucible. A cylindrical alumina-based crucible (99.68% AI2O3, 0.07% SiO 2 , 0.08% Fe 2 O 3 , 0.04% CaO, 0.12% Na 2 O 3 ; 4.5" O.D.
  • X 3.75" LD. X 14.5" depth of a 100-pound induction furnace reactor (Inductotherm) fitted with a 73 -3 OR Powertrak power supply.
  • the induction coil attached to the power supply had the following dimensions: 1 foot 3 inch O.D. by 1 foot 1 inch LD.
  • the total coil height was 1 foot 5 inches.
  • the active zone of the coil comprised 8 active wraps with a total height of 1 foot 1 quarter inch.
  • the top inactive wrap is 2.249 inches above the top active wrap.
  • the bottom inactive wrap is 2.725 inches below the bottom active wrap.
  • the reactor was charged with 9080 g copper (99.98% purity) through its charging port.
  • the reactor was fitted with a graphite cap and a ceramic liner (i.e., the crucible, from Engineering Ceramics). During the entire procedure, a slight positive pressure of 100%Ar ( ⁇ 0.5 psi) was maintained in the reactor using a continuous backspace purge.
  • a ceramic liner i.e., the crucible, from Engineering Ceramics.
  • the induction furnace power was then initiated.
  • the reactor was programmed to heat to 2462 0 F over a 16.5-hour time frame, at a rate no greater than 150°F/hr, as limited by the integrity of the crucible.
  • the induction furnace operated in the frequency range of 0 kHz to 3000 kHz, with frequency determined by a temperature-controlled feedback loop implementing an Omega Model CN300 temperature controller.
  • a three-hour hold was programmed in to match the conditions of run RO 14-02-005. Again, as in run RO 14-02-005 , the bath temperature was unable to reach the saturation temperature of 2462 0 F even after applying full power - 40 Kw - for three hours.
  • Figures 1A-1H illustrates the bath temperature and power during the run.
  • the figures illustrate the cyclic processing incurred during the initial heating of the induction furnace, which was sufficient to tailor the product.
  • ⁇ means that the concentration is ⁇ 20 ppm
  • ⁇ 2e means wt% ⁇ 2 ⁇ tdErr.
  • JOB.785 ⁇ pectrometers configuration ARL 8410 Rh 6OkV LiF220 LiF420 Gelll TlAP
  • ⁇ means that the concentration is ⁇ 20 ppm
  • ⁇ 2e means wt% ⁇ 2 ⁇ tdErr.
  • Sample Height 5 mm ⁇ means that the concentration is ⁇ 20 ppm ⁇ 2e means wt% ⁇ 2 ⁇ tdErr.
  • ⁇ means that the concentration is ⁇ 20 ppm
  • 40 ⁇ 2e means wt% ⁇ 2 ⁇ tdErr.

Abstract

La présente invention concerne des matériaux personnalisés, particulièrement des métaux et des alliages, ainsi que des procédés de fabrication de tels matériaux. Les nouvelles compositions de matière montrent un ordonnancement à long terme et un caractère électronique unique.
PCT/US2009/062662 2008-10-30 2009-10-30 Composition de personnalisation de matière : système ia WO2010051395A1 (fr)

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US10844483B1 (en) 2019-12-16 2020-11-24 Quantum Elements Development, Inc. Quantum printing methods
US11484941B2 (en) 2020-12-15 2022-11-01 Quantum Elements Development Inc. Metal macrostructures
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