US3399981A - Tungsten-rhenium alloys - Google Patents

Tungsten-rhenium alloys Download PDF

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US3399981A
US3399981A US634434A US63443467A US3399981A US 3399981 A US3399981 A US 3399981A US 634434 A US634434 A US 634434A US 63443467 A US63443467 A US 63443467A US 3399981 A US3399981 A US 3399981A
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tungsten
rhenium
particles
temperature
alloy
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Daniel J Maykuth
Elmo P Bergeron
John H Pearson
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Honeywell International Inc
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Allied Chemical Corp
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Priority to AT388268A priority patent/AT281440B/de
Priority to FR1574111D priority patent/FR1574111A/fr
Priority to NL6805774A priority patent/NL6805774A/xx
Priority to GB09475/68A priority patent/GB1188088A/en
Priority to DE19681758220 priority patent/DE1758220A1/de
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/045—Alloys based on refractory metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/28—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from gaseous metal compounds
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0031—Matrix based on refractory metals, W, Mo, Nb, Hf, Ta, Zr, Ti, V or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/08—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal halides
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/923—Physical dimension
    • Y10S428/924—Composite
    • Y10S428/926—Thickness of individual layer specified
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S75/00—Specialized metallurgical processes, compositions for use therein, consolidated metal powder compositions, and loose metal particulate mixtures
    • Y10S75/95—Consolidated metal powder compositions of >95% theoretical density, e.g. wrought
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12181—Composite powder [e.g., coated, etc.]
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12611—Oxide-containing component
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12639—Adjacent, identical composition, components
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
    • Y10T428/12812—Diverse refractory group metal-base components: alternative to or next to each other

Definitions

  • HEATER MEANS (l2) PURIFIED INERT GAS OR HYDROGEN PURIFIED HYDROGEN TUNGSTEN HEXAFLUORIDE 2% RHENIUM HEXAFLUORIDE PAR'HCLES INVENTORS DANIEL J. MAYKUTH ELMO P. BERGERON JOHN H. PEARSON United States Patent 3,399,981 TUNGSTEN-RHENIUM ALLOYS Daniel J. Maykuth, Columbus, Ohio, Elmo P. Bergeron, Baton Rouge, La., and John H. Pearson, Glen'Rock, N.J., assignors to Allied Chemical Corporation, New York, N.Y., a corporation of New York Filed Apr. 25, 1967, Ser. No. 634,434 Claims. (Cl. 29182.2)
  • Alloys of tungsten and rhenium in the form of particles having a microstructure consisting essentially of from 0.5 to 25.0% by weight of rhenium are prepared by vapor phase reduction of tungsten hexafluoride and rhenium hexafluoride.
  • the alloys may be worked into products useful, e.g., in rocket components.
  • Tungsten-rhenium alloys prepared by vacuum-consumable-arc or electron beam melting of pressed and sintered electrodes of tungsten and rhenium powders orother powder metallurgical processes have beenre'portedin the literature.
  • these tungsten-rhenium alloy-s generally fail to retain acceptable bend and low-temperature tensile ductility when subjected to ahigh temperature experience, thereby rendering them unsuitable in various high temperature applications.
  • the fine-grain microstructure of the particles is retained substantially unimpaired throughout consolidation and working of the new tungsten particles and their discrete, consolidated and wrought forms exhibit exceptional resistance to crystal growth or grain growth (hereinafter referred to as recrystallization), under conditions which actively promote these processes in tungsten metal.
  • recrystallization exceptional resistance to crystal growth or grain growth
  • tungsten hexafluoride and rhenium hexafluoride in their vapor phase are reduced in the presence of an excess of hydrogen in a fluidized bed of re fra ctg ry metal gr regfracgory metalpxide sg e d pp rt iples which may be 5 microns average" diameter or larger, and preferably at least 50 microns average diameter or larger, at a temperature suflicieutly high to effect reduction of the tungsten hexafluoride and rhenium hexafluoride to metal.
  • the seed particles are maintained at a temperature of at least 400 F. in a fluidized state.
  • the produced tungsten-rhenium metal alloy deposits uniformly upon the refractory metal or refractory metal oxide seed, producing, as the reaction progresses, particulate product having the 5mm a gmwingsmatrixeoimewly formed tungsifinz lmhllll wfilloy;
  • the deposited tungsten-rhenium alloy may be of controlled high purities, purities of 99.98% by weight and higher being readily achieved.
  • Flow of hydrogen, tungsten hexafluoride and rhenium hexafluoride through the bed at velocities which maintain the growing particles fluidized therein is continued and the growing particles are maintained in the bed until the resulting roughly spherical particles have reached desired size, for example 10 to 10,000 microns.
  • Convenient final particle sizes for handling for recovery purposes and for consolidation are in the range of 200 to 600 microns.
  • the final particle diameter may be from 2 to 3 times the average diameter of the seed, preferably at least 4 times, and up to or several hundred times the seed diameter.
  • the upper limit of size of particulate product is only that at which it becomes impossible or inconvenient to maintain fluidized conditions with concomitant continuing growth of the particles.
  • the seed particles employed in the process of the present invention may constitute a refractory metal or a refractory metal oxide.
  • fractory metal it is intended that all metals which are recognized as refractory in nature and which, in a pure state have a melting point above about 1500 C. be included.
  • Suitable refraggry metalsgedmliicles employed herein include tungsten, tantalum, niobium, molybdenum, rhenium, mixtures and alloys thereof, and the like.
  • the seed particles are of tungsten or of tungstenrhenium produced in a previous run of the process of the development.
  • Suitable refractory metal oxide particles which may be employed as the seed particles include magnesia, thoria, alumina, zirconia, beryllia, yttria, urania, titania, chromia, rare earth oxides, mixtures thereof, and the like.
  • Other useful refractory particles include tungsten carbide, zirconium carbide, and their borides, or nitrides, and the like.
  • tion characteristically have a metallic luster and consists essentially of a core of refractory metal or refractory metal oxide seed particles having deposited thereon an extremely fine-grain microstructure of the novel tungstenrhenium alloy, said microstructure consisting essentially of from 0.5% to 25.0%, preferably 2.0% to 10.0%, by weight of rheniurn, the balance being comprised of tungsten.
  • This microstructure is typically comprised of (1) columnar grains having width and thickness not greater than about 4 and 12 microns, respectively, radially oriented from a seed particle of a refractory metal or a refractory metal oxide and/or (2) grains composed of concentric annular rings not greater than about 2 microns in thickness oriented around the seed particle of refractory metal or refractory metal oxide.
  • the seed particle is tungsten produced by reduction of tungsten hexafiuoride or the unique product of the invention, as is preferred for realization of optimum properties
  • the characteristic fine-grain microstructure desirably extends through the entire particle.
  • the novel particulate product may be consolidated directly into predetermined shape without working, and the consolidated shape may be metallurgically worked, to
  • the novel tungsten-rhenium alloy in its particulate form retains essentially its original microstructure after being subjected to a time-temperature history of about 3270 F. for about one hour.
  • the novel tungstenrhenium particles exhibit exceptionally high hardness, above 1,000 KHN, Knoop hardness number), as produced, and usually at least about 600 KHN after being exposed to about 2900 F. for about one hour and have densities of at least 95%, usually 97% or more of the theoretical density of said tungsten-rhenium alloy.
  • the tungstenrhenium alloy particles of the invention are form'able directly into shapes of desired size and configuration, cored or otherwise, for example, bars or billets which may readily be worked as by rolling, swaging or forged into sheet bars, billets, and the like, or extruded into wire or which are capable of machining directly to a finished shape.
  • the gas-pressure bonded shape may be machined directly at temperatures substantially below ductilebrittle transition temperatures into a finished shape.
  • the final fabricated products, whether wrought or not, are of high tensile strength and possess unexpected and outstanding ductility, retention of tensile strength, hardness and ductility upon exposure to high temperature service conditions and a remarkable resistance to crystal growth or recrystallization under high temperature service conditions.
  • Products made from the particles of the invention retain ductility to a surprising extent after time-temperature histories which would be expected to substantially destroy usable ductility.
  • wroughtt sheet of the tungsten-rhenium alloy particles of the invention after exposure to about 3000 F. for about one hour, characteristically exhibit 'a ductile-brittle transition temperature (4T) below about 300- F., and generally below about 150 F.; these ductile-brittle transition temperatures are retained even after 95% or more conversion by temperature treatment of original fine-grain microstructure into large-grain equiaxed crystal.
  • consolidated bodies prepared from the tungstenrhenium alloy granules of the invention characteristically exhibit, at a temperature of about 77 R, an ultimate tensile strength of at least 100,000 p.s.i., a yield strength between about 60% and 98% of said ultimate tensile strength and a measurable tensile elongation in one inch of at least.1%, after exposure to a stress relief anneal of one hour at about 1800 F., and exhibit, at a temperature of about 300 R, an ultimate tensile strength of at least 50,000 p.s.i., a yield strength between about 60% and 98% of said ultimate strength and a measurable tensile elongation in one inch of at least 1%, after exposure to a stress relief anneal of one hour at about 3600 F.
  • a Vickers hardness number (under a 10 kilogram load) of at least 425, after being subjected to an anneal of about 2750 F. for about one hour, is characteristic of consolidated bodies prepared from the tungsten-rhenium alloy granules of the invention, previously. described.
  • the consolidated forms prepared from the tungsten-rhenium granules of the invention'resist recrystallization on anneals which ordinarily recrystallize at least surfaces of consolidated forms composed of unalloyed tungsten obtained by reduction of tungsten hexafluoride and completely recrystallize consolidated forms prepared from tungsten-rheniurn alloys obtained by above referred to prior art procedures.
  • consolidated forms prepared from the tungstenrhenium alloy particles of the present invention exhibit, when sheet rolled at about 2650 F., a recrystallized surface layer less than about 1.0 mil thick after exposure to about 3250 F. for about one hour and less than about 1.5 mil thick after exposure to about 3600 F. for about one hour.
  • FIGURES 1 through 4, inclusive, are photomicrographs illustrating the metallurgical microstructure of as-produced tungsten-rhenium alloys of the present invention having a rheniurn content of 1.0%, 2.5%, 10.0% and 20.0%, by weight, respectively;
  • FIGURES 5 through 8, inclusive are photomicrographsillustrating the metallurgical microstructure of the particulate as-produced tungsten-rhenium alloys illustrated in FIGURES 1 through 4 after being subjected to severe time-temperature conditions;
  • FIGURES 9 through 12, inclusive are photomicrographs illustrating the metallurgical microstructure of the particulate as-produced tungsten-rhenium alloys illustrated in FIGURES 1 through 4 after gas-pressure bondmg;
  • FIGURES 13, 15 and 17 are photomicrographs illustrating the metallurgical microstructure of wrought tungsten-rhenium products of the invention having a rheniurn content of 1.0%, 4.0% and 10.0%, by Weight, respective y;
  • FIGURES 14, 16 and 18 are photomicrographs illustrating the metallurgical microstructure of the wrought novel products illustrated in FIGURES 13, 15 and 17, after being subjected to severe time-temperature condi tions;
  • FIGURES 19 and 20 and FIGURES 21 and 22 are photomicrographs illustrating, for comparison purposes, the metallurgical microstructure of wrought tungstenrhenium alloys having a rhenium content of 1.85% and 3.55%, by weight, respectively, prepared by a conventional procedure, in as-produced condition (FIGURES 19 and 21) and after being subjected to severe time-tcmperature conditions (FIGURES 20 and 22);
  • FIGURE 23 illustrates graphically the comparison of bend-transition temperature (4T) of wrought product of the invention and of wrought tungsten-rhenium alloys, prepared by a conventional procedure, after being subjected to a severe time-temperature condition;
  • FIGURE 24 is a diagrammatic illustration of an apparatus for practicing the process of the invention.
  • the diagram omits many auxiliary items, such as reactant storagetanks and purification systems, valves, flow meters, pressure gages, safety traps, temperature controls, thermocouples and the like, although the use and application of such items will be obvious and readily apparent to one skilled in the art.
  • FIGURES 1 through 4 are photomicrographs, at a magnification of about 187 times, of as-produced tungsten-rhenium particles of the invention, produced by hydrogen reduction of tungsten hexafluoride and rhenium hexafluoride in a fluidized bed of tungsten seed particles, obtained by reduction of tungsten hexafluoride in a fluidized bed.
  • the photomicrographs include a cross-sectional view of at least one as-produced particle as Well as of portions of neighboring granules mounted in a hardened plastic base.
  • FIGURES 1 through 4 The as-produced granules of FIGURES 1 through 4 are similar in that they show the deposited metal occurring in the form of concentric annular rings, which tend to be slightly wider (about one micno thick) in the granules of lowest rhenium content.
  • the prominent band structure is attributed to cyclic deposition in the fluidized bed reactor and variation in the bands 'to statistical variations in circulation therein.
  • the band structure, as well as the coalescence of seed particles, may be avoided in fluidized bed runs wherein seed circulation and reaction temperatures at which the seed is introduced are more closely controlled.
  • the novel tungsten-rhenium alloy granules depicted in FIGURES 1 through 4 are of density of at least about 95% of the theoretical density of said alloy and have a hardness :of 1016, 1142, 1346 and 1307 KHN, respectively; a control sample of unalloyed tungsten prepared by hydrogen reduction of tungsten hexa-fluoride showed a hardness of 960 KHN.
  • the individual radially oriented tungsten-rhenium crystals average about 1.5 microns in width and about 6 micnons in length.
  • the thickness of the concentric annular rings is about 1 micron.
  • FIGURES 5 through 8 are photomicrographs, at magnifications of 187 times, of the tungsten-rhenium particles illustrated in the as-produced condition in FIGURES 1 through 4, respectively, after being exposed to a temperature of about 3270 F. for about one hour.
  • annealing temperatures between about 2200 F. and 3300 F. the concentric annular rings evident in FIGURES 1 through 4, are replaced by anextremely fine-grain structure which is clearly evident from FIGURES 5 through 8.
  • the temperature at which the rings disappeared was proportional to rhenium content, being about 2550 F. for granules having a rhenium content up to about 5.0%, about 2900' F. for granules having a rhenium content between about 5.0 and 10.0%, and above about 2900 F. for granules having -a rhenium content above about 10.0% by weight.
  • rhenium content is proportional to rhenium content, being about 2550 F. for granules having a rhenium content up to about 5.0%, about 2900' F. for granules having a rhenium content between about 5.0 and 10.0%, and above about 2900 F. for granules having -a rhenium content above about 10.0% by weight.
  • the tungsten-rhenium alloy particles of the invention are convertible directly into dimensionally stable, strong ductile, predetermined shapes having the above enumerated properties.
  • One method of producing such bodies involves placing the tungsten-rhenium alloy particles in a gastight, thin walled container of predetermined shape and dimension, packing the same by vibration, to desired extent, for example, to a bulk density of 65 percent or more of the theoretical density of tungsten-rhenium alloy, evacuating the container, and then subjecting the evacuated gas-tight container to gas pressure, time and temperature adequate to deform the container material and cause it to flow inwardly and compress the tungsten particles until they become consolidated into a unitary mass.
  • the gas is one which, considering the conditions and container metal employed, will not penetrate the latter.
  • Armco iron, Zircaloy and molybdenum containers my be used with helium or argon as compressing gas under 5,000 to 20,000 pounds per square inch while maintaining the container and contents at annealing temperatures for tungsten-rhenium alloy consistent, of course, with the maintenance of the integrity of the encasing envelop as a gas-tight unit.
  • Suitable temperatures considering the limitations of the encasing envelop and pressure, may be in the range of about 2000 F. to about 3500 F. and above. The time necessary may vary from several minutes to several hours, depending upon the temperature used and the density of shaped product desired.
  • the bonding process involves deformation or flow of the individual particles to decrease interstitial volume and increase area of contact between the discrete particles, accompanied and followed by development of metallurgical bond between the particles by intercrystallization between the contiguous interfaces.
  • the deformation processes proceed easily to a substantially impervious product (92% or higher of the theoretical density of tungsten-rhenium alloy) at times of the order of 4 hours or less, in many instances, of the order of two hours.
  • the tungsten-rhenium particles of the invention are remarkably resistant to crystal growth upon being subjected to temperatures for times in excess of times required to anneal conventional compacted and sintered tungsten-rhenium alloy powders.
  • maximum tensile strength is obtained if excess of times, i.e., times beyond those required to produce the interparticulate crystallization, are not employed.
  • the worker skilled in the art can, with a minimum of experimentation, determine the optimum composition of encapsulating metal, time, temperature and pressure to suit the purpose of the projected use of shaped bodies of the invention.
  • FIGURES 9 through 12 illustrate, at magnifications of 187 times, sections of typical consolidated shapes produced by gas pressure bonding from tungsten-rhenium particle products of the invention having a rhenium content of 1.0%, 2.5%, 10.0% and 20.0%, by weight, respectively.
  • the shapes were made by the above described technique using 10,000 pounds per square inch of helium pressure on a molybdenum capsule containing essentially spherical tungsten-rhenium particles of about 200 to 400 microns size for about 3 hours while maintaining the unit at about 2900" F.
  • the particles used to prepare these shapes, as well as their method of preparation were described above in discussion with FIGURES 1-4.
  • the particulate tungsten-rhenium alloy of the invention is unique in that the final dimensions of pressure-bonded shapes made directly from the particles are so accurately predictable, the density through the pressure-bonded shape so uniform, and the strength of units such that the entire pressure-bonding operation may be confidently conducted for the purpose of yielding a pressure-bonded unit, which. without working or other processing (except possibly chemical removal of the encapsulating metal) needs only finished machining to produce a satisfactory final product.
  • Nozzle and cone shapes are typical of those which can be produced in this way, with finished machining only to remove a few thousandths of an inch of metal from the gas-pressure-bonded shapes.
  • the pressure bonded shapes, with or without prior removal of the encapsulating metal, as by leveling with acid, may be worked by conventional metallurgical techniques such as by rolling, forging, drawing, swaging, spinning and the like under conditions suitable for making wrought tungsten-rhenium alloy.
  • rolling or forging for example, several passes may be employed at conditions to give controlled reduction, which may be uniform, say to per pass, or to decreasing or increasing extent.
  • Encapsulating metal may be removed after completion of the working or after any desired pass.
  • Working of consolidated bodies of particles of the invention may be carried out at relatively low temperatures in significantly lower than ordinarily employed with, or sometimes even suitable for, fabrication of tungsten-rhenium alloys prepared by conventional arc-melting or electron-beam melting methods referred to above.
  • the breakdown pass may be at temperatures substantially below 3000 F. and, in fact, for optimum development of the wrought properties of the alloy,
  • tungsten-rhenium alloy prepared by the above described conventional methods, often requires, for optimum development of metallurgical properties, working temperatures several hundred degrees higher, up to 400 F. or more higher, than those indicated.
  • the resulting wrought product is, moreover, structurally inferior than those made possible by the present invention.
  • the product of the invention provides for substantial economies of wrought material in manufacture of items meeting structural specifications, as well as superior products.
  • FIGURES 13 through 23 Superiority of the tungsten-rhenium particles of the invention is further illustrated by FIGURES 13 through 23.
  • FIGURES 13, 15 and 17 are photomicrographs at magnification of 187 times of as-rolled sheet stock, pressure bonded novel spherical particles of the invention having 1.0%, 4.0% and 10.0%, by weight, rhenium content, respectively, the sheets illustrated in FIGURES l3 and 15 being rolled to 93% reduction at a rolling temperature of about 2900 F. and the sheet illustrated in FIGURE 17 being rolled to reduction at a rolling temperature of about 2650 F.
  • FIGURES 14, 16 and 18 are photomicrographs at magnification of 187 times of the sheet stock illustrated in FIGURES 13, 15 and 17 after being heated for about one hour at a temperature of about 3260 F.
  • FIGURES 19 and 21 are photomicrographs (187 times) of as'rolled tungsten-rhenium alloy sheet stock having a rhenium content of 1.85% and 3.55%, by Weight respectively; these sheet alloys were prepared from a blend of 325 mesh commercially pure (undoped) tungsten powder and -200 mesh commercially pure rhenium powder which was compacted into electrodes, sintered at 4100 F. and consolidated by triple electron-beam-melting.
  • FIGURES 20 and 22 are photomicrographs at magnification of 187 times of the sheet stock illustrated in FIGURES 19 and 21 after being heated for about one hour at a temperature of about 3250 F. These rolled products were fully softened, exhibiting Vickers hardnesses (under a 10 kilogram load) of 361 and 325, respectively, and were each fully recrystallized.
  • FIGURES 13 through 18 show that the Wrought form of the tungsten-rhenium alloy particles of the invention retains a significantly greater proportion of fine-grained structure than the wrought tungsten-rhenium alloys prepared by conventional procedures after extreme temperature exposure.
  • FIGURES 20 and 22 show that the wrought product made from electron-beam melted tungsten-rhenium alloys after high-temperature service became essentially completely recrystallized.
  • FIGURES 14, 16 and 18 demonstrate that wrought product made from particles of the invention resists recrystallization during high-temperature service to outstanding degree, retaining to surprising extent after such service original crystal structure and, hence, tensile strength, ductility, workability and utility for service of this type.
  • the retention of strength and hardness after high-temperature service, as well as superior strength throughout an extended high-temperature range permit substantial economies of alloy and consequently of weight for structures intended for high-temperature service.
  • FIGURE 23 illustrates the changes in the minimum temperature at which a rolled sheet, which has been subjected to a temperature of about 3000 F. for one hour, may be bent without cracking over a are having a radius of four times sheet thickness. It is evident from FIGURE 23 that fabricated products of the invention (represented by Curve A) retain values in this respect below 300 F., and usually below about F., despite time-temperature histories which normally result in from substantial to essentially complete recrystallization.
  • rolled sheet made from electron-beam melted tungsten-rhenium alloys prepared in the above described manner require a substantially higher rhenium content, generally at least about five times higher, on a weight basis, as required by fabricated products made from tungsten-rhenium alloys of the present invention.
  • a sheet rolled product produced from tungsten-rhenium alloy of the invention having a rhenium content of about 4.0%, by weight exhibited a bend transition temperature (4T) of about 104 F. after annealing for one hour at 3000 F.
  • tungsten-rhenium alloy products of the present invention characteristically reflect excellent low-temperature tensile ductility both as rolled and after annealing to high temperatures.
  • Tensile properties (determined by ASTM E857T and E2l-58T) of representative sheet alloys produced from tungsten-rhenium alloy particles of the invention and of sheets made from electron-beam-melted tungsten-rhenium alloys are summarized in Table I, below, all sheet samples being electropolished prior to testing.
  • the material designated as, A represents sheet produced tfrom tungstenrhenium alloy particles of the invention having a rhenium content of 4.0%; the material designated as, B, represents sheet produced from electron-beam-melted tungstenrhenium alloy particles having a rhenium content of 1.85%; and the material designated as, C, represents sheet produced from electron-beam-melted tungsten-rhenium alloy particles having a rheniumpontent of 3.55%.
  • TABLFl I material which does not react with the reactants.
  • Suitable metals include high nickel content alloys of copper and Ultimate Yield Test Tem- Tensile Strength Elongation Material Test Conditlon perature Strength, (0.2% percent in F.) 10 psi. offset) one, inch (10 p.s.i.)
  • a unique property of tungsten-rhenium particles of the invention resides in the fact that by a single step, gaspressure bonding as described above, the particles may be converted to a solid unit of predetermined size and shape having density which may approach the theretical density of tungsten-rhenium alloy. If the optimum in strength is desired, density of the shape should be 92% or higher of theoretical.
  • These consolidated-only products have structural and other properties of wrought products made therefrom and, like wrought tungsten-rhenium products produced therefrom, may be cold machined directly into a desired finished shape having said service characteristics, for example, those required in high-temperature services, for example, in rocket components, such as nose cones on missiles in atmospheric re-entry applications or as in uncooled rocket nozzles.
  • Sintered tungsten-rhenium powder shapes even though carefully prepared under conditions yielding a sinter of maximum density, do not possess such properties.
  • the high density bonded particles of the invention are so uniform in structure and have dimensional predictability of such a high order that in many instances the bonded shape as produced requires only finish machining.
  • tungsten-rhenium products of the invention lies in the ability of rolled sheet produced from such particles to retain ductile-brittle transition temperature below about 300 F. or less, even after essentially complete conversion by temperature treatment of original fine-grained microstructure into "large-grained equiaxed crystal.
  • Such material is capable of withstanding thermal shock de'spite'its essentially complete recrystallization, as are unrolled substantially completely recrystallized gas-pressure bonded shapes.
  • the improved high-temperature properties of the" tungsten-rhenium alloy particles of the present invention render products prepared therefrom amenable to fabrication into a variety of useful sheet metal shapes with a minimum of difliculty; for example, there is no need for elaborate hot-form equipment/These shapes include specific articles such' as curved leading edge members for wings on control surfaces on re entry space vehicles, channel or corrugated structural panels as' supports for high temperature application's,'flat or contoured skins for hot structures such as entrance caps for solid fueled rocket nozzles.
  • FIGURE 24 of the drawings illustrates one mode of effecting the process of the invention in which there is shown a reactor, generally designated 3;of a suitable nickel such as Monel metal. Copper is a useful material for inlet and exit lines. Tetrafluoroethylene polymers and chlorotrifluoroethylene polymers are useful for gaskets and for flexible lines.
  • the reactor 3 comprises a vertical tubular-shaped section 4 providing a reduction zone '5, tapered into lower conical section 6 and flaring gradually outward into an upper section 7 which is closed by a top 8 which may be provided with a suitable safety vent 15.
  • Lines 9 and 10 are provided to introduce the reactants, hydrogen, tungsten hexafluoride and rhenium hexafluoride, into the system to flow as a mixture into lower conical section 6, and upwardly through reduction zone 5.
  • Line 11 is provided through top 8 to introduce refractory metal or refractory metal oxide seed particles into reactor 3, wherein they drop into the reduction zone 5.
  • Heater means 12 such as electrical resistance coils, or induction heaters, or a gas fired furnace, surrounding the reduction zone, heat the particles therein and maintain them at a suitable temperature for the hydrogen reduction of tungsten hexafluoride and rhenium hexafluoride.
  • action temperature may be in the range of about 400 F. up to a temperature of 2000 F. or somewhat higher.
  • temperatures substantially above this level accrues by use of temperatures substantially above this level.
  • use of the process has demonstrated that quite satisfactory commercial operating temperatures lie in the range of about 1000 F. to 1200 F., as for example about 1100" F. to 1150 F.
  • temperatures below about 1200 F. or with low excesses of hydrogen substantial quantities of unconverted tungsten hexafluoride and/or rhenium hexafluoride tend to exit the reaction zone.
  • the upwardly flowing hydrogen, tungsten hexafluoride and/or rhenium hexafluoride, and, as it is produced, hydrogen fluoride function to fluidize the seed particles.
  • the volume of hydrogen greatly exceeds the volume of tungsten hexafluoride and rhenium hexafluoride and hence serves as the primary'fluidizingcomponent at the outset of the reaction, its eflfect being augmented by produced hydrogen fluoride.
  • the tungsten hexafluoride and rhenium hexafluoride are reduced to tungsten metal and rhenium metal which deposit on the fluidized metal seed particles producing, by growth to predetermined extent, the unique tungsten-rhenium alloy particles of the invention.
  • the gases exit expanded upper section7, the resulting decrease in their velocity is to below fluidizing level; hence, the lower end of section 7 defines the upper level of the fluidized bed.
  • the gases exit the reactor by upper discharge line 14. At this point they might contain finely divided solids which may be separated from them and returned to the reactor by known means.
  • the reactor may be operated on abatch basis or with continuous introduction of seed and continuous withdrawal of produced particles from the fluidized bed, for example, at a level adjacent the bottom, as throughline 13.
  • the continuously withdrawn particles are then pref- 1 1 erably subjected, possibly after purging of accompanying gas therefrom, to desired classification procedure to generate out finished product of desired size. Smaller particles are then returned to the reactor, for example, with the feed or fresh seed.
  • FIGURE 24 is primarily adapted quantity of fluorine, the form of which is not known, exfor batch operation, in which feed of hydrogen, tungsten cept occurrence as fluoride ion.
  • hexafiuoride and rhenium hexafiuoride is initiated through As indicated hereinabove, the quantity of hydrogen gas a precharged bed of refractory metal or refractory metal employed must be in excess of the stoichiometric equivoxide seed and maintained for times, depending upon realent of the tungsten hexafiuoride and rhenium hexaaction temperatures and proportion of feed components fluoride feed. The extent of the excess required to effect selected, which will produce the desired size of product Complete reduction of these metal hexafiuorides to metal particle. At the end of that time, which can be selected tends to be a function of reaction temperatures.
  • the feeds for select1on of satisfactory proportionate quantities of are discontinued and the reactor is purged of combustible l5 reactants may be the fraction represented by one-third of and corrosive substances by inert gas, typically argon the number of moles of hydrogen fed over the total of or helium, admitted through line 16.
  • inert gas typically argon the number of moles of hydrogen fed over the total of or helium, admitted through line 16.
  • the tungsten product the number of moles of tungsten hexafiuoride and rhenium may then be withdrawn through line 13 immediately or hexafiuoride feed.
  • the mole ratio F At temperatures of the order of 400 after a desired cooling period. in general, the mole ratio F.
  • fraction should be about 50 or higher, at 1000 of rhenium hexafiuoride to total metal hexafiuoride, i.e., F. to 1200 F. about 10 or higher and at 1825 F. and tungsten hexafiuoride plus rhenium hexafiuoride, charged higher may be 1.5 to 2 or higher.
  • into the reaction zone may range from about 0.01 to Specific examples of the invention are summarized in 0.50 or higher, although mole ratios of rhenium hexa- Table 11.
  • the exhaust gases are preferably processed by fluoride and rhenium hexafiuoride to the bottom of the techniques which will be apparent to those skilled in the reactor, adjusting the feed of hydrogen to about M; cubic art to separate hydrogen in very dry air-free form for feet per minute standard conditions and the feed of tungreuse and, if it is present, to recover tungsten fluoride sten hexafiuoride and rhenium hexafiuoride to maintain and/or rhenium fluoride.
  • Products of this quantity of tungsten and rhenium in the original hexa purity and, in fact, of purity of 99.95% or more tungstenfluoride feed to the extent tabulated, the deposition having rhenium, by weight, may be readily obtained by using been made at the rate persquare foot of reactor area distilled tungsten hexafiuoride and rhenium hexafiuoride shown. sold commercially and hydrogen diffused through pal- Upon beginning operation, the particles of seed plus ladium.
  • the product contains characteristically the iminitially deposited tungsten and rhenium conform roughly purities present in tungsten-rhenium alloys produced by in shape to that of the seed granules.
  • tungsten and rhenium of the type deposited by the process of the invention should constitute at least the predominant proportion of the final particulate product.
  • the final particles are all or substantially all constituted by the normal deposited tungsten and rhenium.
  • deposition should be continued until deposited tungsten-rhenium 1 aggregates at least double the weight of the seed.
  • Example 1 Continuing the process under the conditions of Example 1 until ultimate particle size is 300 to 400 microns results in product in which the average particle contains a tungsten-rhenium deposit of about 92 to about 97 percent by weight of product made during the run, while continuing until ultimate particle size is about 600 microns results in product in which the average particle size contains a tungsten-rhenium deposit of greater than 99 percent by weight of product made during the run.
  • a tungsten-rhenium alloy in the form of substantially spherical particles consisting essentially of a microstructure of (1) columnar grains having width and thickness not greater than about 4 and 12 microns, respective- 2.
  • the alloy of claim 1 in which said particles, upon gas-pressure bonding at about 10,000 p.s.i. and about i 2900" F. for about 3 hours, yield a unitary consolidated body of at least 92% of the theoretical density of said alloy, said consolidated body being rollable to 80-95% reduced product having a ductile-brittle transition temperature below about 300 F. after exposure to about 3000 F. for about one hour.
  • body is characterized by exhibiting, when sheet rolled at about 2650 F., a recrystallized surface layer less than about 1.0 mil thick after exposure to about 3250" F. for about one hour and less than about 1.5 mil thick after exposure to about 3600 F. for about one hour.
  • a tungsten-rhenium alloy in the form of substantially spherical tungsten-rhenium particles of 10 to 10,000 microns diameter said particles consisting essentially of a microstructure of (1) columnar grains havingwidth and thickness not greater than about 4 and 12 microns, respectively, radially oriented from a seed particle of a refractory metal or a refractory metal oxide, and/or (2) grains composed of concentric annular rings not greater than about 2 microns in thickness oriented around the seed particle of refractory metal or refractroy metal oxide, said microstructure (21) consisting essentially of from 2 to 10% by weight of rhenium, the balance being tungsten, (b) having density of at least 95% the theoretical density of said alloy and (c) exhibiting essentially said microstructure upon being subjected to about 3270 F.
  • saidseed particle is of an alloy of tungsten and rhenium containing between about 0.5% and 25.0% by weight of rhenium and said consolidated body is rollable to 8095% reduced product having a ductile-brittle transition temperature below about 150 F. after exposure to about 3000 F. for about one hour.

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US3637374A (en) * 1968-05-27 1972-01-25 Fansteel Metallurgical Corp Method of producing tungsten rhenium alloys by chemical vapor deposition
US3829969A (en) * 1969-07-28 1974-08-20 Gillette Co Cutting tool with alloy coated sharpened edge
US5415707A (en) * 1993-10-05 1995-05-16 Ethicon, Inc. High modulus materials for surgical needles
US20050238522A1 (en) * 2004-04-22 2005-10-27 Rhenium Alloys, Inc. Binary rhenium alloys
US20070084309A1 (en) * 2005-10-19 2007-04-19 Yuji Akimoto Method for manufacturing rhenium-containing alloy powder, rhenium-containing alloy powder, and conductor paste
US20090082763A1 (en) * 1999-06-22 2009-03-26 Senorx,Inc. Shapeable electrosurgical scalpel
CN103469043A (zh) * 2013-09-18 2013-12-25 赵福来 助水燃烧合金及其应用
US10137502B1 (en) * 2006-10-20 2018-11-27 Utron Kinetics, LLC Near net shape combustion driven compaction process and refractory composite material for high temperature applications
CN112522519A (zh) * 2020-12-04 2021-03-19 合肥工业大学 一种从钨铼合金废料中分级分离和回收金属铼的方法
CN113088752A (zh) * 2021-03-31 2021-07-09 五矿铍业股份有限公司 一种铍铜母合金的制备方法
CN113798504A (zh) * 2021-09-17 2021-12-17 郑州大学 3d打印用稀土氧化物弥散增强钨粉的制备方法
CN114918270A (zh) * 2022-04-14 2022-08-19 成都虹波实业股份有限公司 一种钨铼合金窄带及其制备方法
CN119703089A (zh) * 2024-12-30 2025-03-28 丰联科光电(洛阳)股份有限公司 一种钼铼合金管旋压制备方法
CN120384215A (zh) * 2025-04-25 2025-07-29 天津大学 一种层状异质结构第二相弥散强化的钨铼细晶合金或钼铼细晶合金制备方法

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FR2523009B1 (fr) * 1982-03-11 1987-01-02 Toho Zinc Co Ltd Procede de production de metaux en poudres fines
JPS59170211A (ja) * 1983-03-14 1984-09-26 Toho Aen Kk 超微粉の製造方法
CN112553489B (zh) * 2020-12-04 2021-09-07 西安交通大学 一种钼铼、钨铼合金废丝的增值回收方法

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US3062638A (en) * 1961-05-03 1962-11-06 Union Carbide Corp Ultrafine metal powders
US3177067A (en) * 1962-06-22 1965-04-06 Wyandotte Chemicals Corp Method of recycling fine refractory metal particles until particles grow to the desired size
US3234067A (en) * 1962-11-05 1966-02-08 Du Pont Process for bonding rubber to polyester shaped structures
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US3637374A (en) * 1968-05-27 1972-01-25 Fansteel Metallurgical Corp Method of producing tungsten rhenium alloys by chemical vapor deposition
US3829969A (en) * 1969-07-28 1974-08-20 Gillette Co Cutting tool with alloy coated sharpened edge
US5415707A (en) * 1993-10-05 1995-05-16 Ethicon, Inc. High modulus materials for surgical needles
US20090082763A1 (en) * 1999-06-22 2009-03-26 Senorx,Inc. Shapeable electrosurgical scalpel
US20050238522A1 (en) * 2004-04-22 2005-10-27 Rhenium Alloys, Inc. Binary rhenium alloys
US20070084309A1 (en) * 2005-10-19 2007-04-19 Yuji Akimoto Method for manufacturing rhenium-containing alloy powder, rhenium-containing alloy powder, and conductor paste
US7503959B2 (en) 2005-10-19 2009-03-17 Shoei Chemical Inc. Method for manufacturing rhenium-containing alloy powder, rhenium-containing alloy powder, and conductor paste
US10137502B1 (en) * 2006-10-20 2018-11-27 Utron Kinetics, LLC Near net shape combustion driven compaction process and refractory composite material for high temperature applications
CN103469043A (zh) * 2013-09-18 2013-12-25 赵福来 助水燃烧合金及其应用
CN103469043B (zh) * 2013-09-18 2015-04-29 赵福来 助水燃烧合金及其应用
CN112522519A (zh) * 2020-12-04 2021-03-19 合肥工业大学 一种从钨铼合金废料中分级分离和回收金属铼的方法
CN112522519B (zh) * 2020-12-04 2023-11-03 合肥工业大学 一种从钨铼合金废料中分级分离和回收金属铼的方法
CN113088752A (zh) * 2021-03-31 2021-07-09 五矿铍业股份有限公司 一种铍铜母合金的制备方法
CN113798504A (zh) * 2021-09-17 2021-12-17 郑州大学 3d打印用稀土氧化物弥散增强钨粉的制备方法
CN113798504B (zh) * 2021-09-17 2023-08-22 郑州大学 3d打印用稀土氧化物弥散增强钨粉的制备方法
CN114918270A (zh) * 2022-04-14 2022-08-19 成都虹波实业股份有限公司 一种钨铼合金窄带及其制备方法
CN114918270B (zh) * 2022-04-14 2023-10-24 成都虹波实业股份有限公司 一种钨铼合金窄带及其制备方法
CN119703089A (zh) * 2024-12-30 2025-03-28 丰联科光电(洛阳)股份有限公司 一种钼铼合金管旋压制备方法
CN119703089B (zh) * 2024-12-30 2025-08-26 丰联科光电(洛阳)股份有限公司 一种钼铼合金管旋压制备方法
CN120384215A (zh) * 2025-04-25 2025-07-29 天津大学 一种层状异质结构第二相弥散强化的钨铼细晶合金或钼铼细晶合金制备方法

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NL6805774A (de) 1968-10-28
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AT281440B (de) 1970-05-25
FR1574111A (de) 1969-07-11

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