US3622406A - Dispersoid titanium and titanium-base alloys - Google Patents

Dispersoid titanium and titanium-base alloys Download PDF

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Publication number
US3622406A
US3622406A US710631A US3622406DA US3622406A US 3622406 A US3622406 A US 3622406A US 710631 A US710631 A US 710631A US 3622406D A US3622406D A US 3622406DA US 3622406 A US3622406 A US 3622406A
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Prior art keywords
titanium
dispersoid
article
percent
boron
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Expired - Lifetime
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US710631A
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English (en)
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Milton B Vordahl
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Titanium Metals Corp
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Titanium Metals Corp
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • 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
    • C22C1/0458—Alloys based on titanium, zirconium or hafnium
    • 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
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • 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
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/268—Monolayer with structurally defined element

Definitions

  • This invention pertains to titanium and titanium-base alloys containing dispersions of particles essentially insoluble in solid titanium at any temperature but soluble in molten titanium, and to methods of producing such dispersoid alloys.
  • the invention pertains to titanium-base alloys containing finely divided particle dispersions of one or more dispersoids selected from the group consisting of boron, thorium, groups lllb and lIlc of the periodic table of elements set forth inside the forth cover of The Merck Index," seventh edition, 1960, published by Merck & Co., Inc., Rahway, New Jersey elements having atomic numbers 57 through H which may be designated rare earth elements, and compounds of the foregoing such as the sulfides as well as combinations of any of them, which are substantially insoluble in solid titanium at any temperature but soluble in molten titanium.
  • the preferred dispersoids are boron, cerium, thorium, lanthanum and combinations and compounds thereof, such as TiB, CeS, LaS, misch metal and other mixed rare earth sulfides, and the like.
  • the rare earths and especially cerium and lanthanum are most preferably used as the sulfides whereas the boron and thorium are preferably used in the elemental form.
  • the method for producing dispersions of the present invention involves melting the components to form a homogeneous liquid preferably thence extreme chill-casting the liquid as by splashing it in thin layers against a cold solid surface or by spraying the liquid into a cold chamber wherein it freezes as fine shot, and finally consolidating the shot and splashings by pressure, heat and plastic deformation into a product of essentially theoretically full density.
  • the dispersoid particle components although soluble in the liquid titanium, are substantially insoluble in solid titanium and are thus forced by freezing of the liquor to separate as particle of extreme fineness because of the very short time available for growth.
  • the dispersoid particles ordinarily appear as submicron-sized dispersions within the shot or splashed flakes which, although fine themselves relative to any standard ingots, are very coarse relative to the dispersoid particles. That is, the shot or flakes may be from perhaps 50 to 100 microns to several hundred microns in mean section, and the dispersed particles therein will be on the order of several microns to less than 1 microns in particles size.
  • the dispersoid as present in the final solid alloy may appear as a compound with one or more of the materials present in the base alloy.
  • the final solid alloy may contain the boron as TiB.
  • reference to the novel base metal alloys of the present invention as including a given dispersoid is to be un derstood as meaning the dispersoid as added irrespective of the form in which it appears in the final product.
  • Alloys containing substantially insoluble, stable and inert particles dispersions, and certain methods of making them are also well-known.
  • the most used conventional method consists of mixing extremely fine powders of base metal and of dispersoids, compacting, sintering and working the mixtures to solidify them.
  • the high reactivity of submicron powders thereof and the ready solubility of contaminants, as for example, oxygen and nitrogen from the air make the powder approach impractical.
  • Shot and flake as described herein have several hundred times less surface per unit mass than conventional powders, and handling is therefore not difficult.
  • the micron or submicron particles exist in the shot and flake as made according to the invention and titanium powder of such small particle size is unnecessary.
  • Another known method of making stable dispersoid systems consists of internal oxidation of solid solutions of active metals in a less reactive base metal, such for example as titanium containing in solid solution, certain rare earth metals which can be oxidized in situ to form stable particles of oxide.
  • a less reactive base metal such for example as titanium containing in solid solution
  • certain rare earth metals which can be oxidized in situ to form stable particles of oxide.
  • the combined requirements of solid solubility of the metallic component of the dipersoid, plus greater reactivity then titanium essentially limits the possibilities for this approach to the rare earths which are soluble in solid titanium.
  • rare earth oxides are stable only in titanium which of itself contains a substantial oxygen content, which is in some instances undesirable.
  • the dispersoids above-mentioned with reference to this invention are all substantially insoluble in solid titanium, and when present as micron or submicron dispersions as produced in accordance with the methods of the invention, impart outstanding elevated temperature creep properties operable to higher temperature levels than is attainable with dispersoid type titanium and titanium-base alloy materials heretofore available insofar as I am aware. Additionally, compositions of the present invention, especially those containing boron as the dispersoid display a substantial resistance to hot salt corrosion cracking. Quick satisfactory results are obtained in this regard at boron inclusions of about 0.25 to about 1 percent.
  • titanium or titanium alloys in the molten state containing about 0.1 to 6 percent in total amounts of one or more elements, compounds or mixtures as aforesaid which are soluble in the molten base metal but insoluble in the solid state thereof are shotted as described for example, in US. Pat. No. 2,897,539.
  • the shot are then consolidated into billets by known methods such as canning and hot pressing.
  • Mill products are made from the hot pressed billets by conventional means as by forging, rolling, extruding, etc.
  • the following table I shows for a Ti-6Al-2Sn-4Zr-2Mo al loy, creep strength with long-term aging without and with an inert submicron dispersoid according to the invention.
  • o percent 5 l have further discovered as an additional feature of the H Loco/3mm present invention that the alloy thereof containing about 6 233%??? 0 igggggfigg 1 percent aluminum, 4 percent vanadium, 1 percent boron and 4sn-10zr+3'U 0.50 1, 000/30 150 the balance substantially titanium, is substantially more reiggjgggggg $ggflg8 g-g sistant to hot salt corrosion cracking than is the alloy without 4sn 10Zr.2MO+1 75 1 ⁇ . 1:000/30/150 1g 50 the boron addition.
  • the boron free, 6 percent Al-4 V alloy 521823 0 31; Sag i'%;ggflgg -g shows severe cracking in less than 100 hours of exposure to 1 '700/110/150 103) salt, NaCl, at 800 F. and under 25 Ks.i. stress.
  • the above boron containing alloy showed no visible 4sn 5zr,nMo+2'Ce 700/110/160 cracking such as degraded ductility in tensile tests after 100 32 35 11 123 Th 7%% fig 0 3 5 hours at 800 F. and at 30, 35, and Ksi.
  • dispersoid is boron, titanium boride, thorium, cerium, cerium sulfide, lanthanum, or lanthanum sulfide.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
US710631A 1968-03-05 1968-03-05 Dispersoid titanium and titanium-base alloys Expired - Lifetime US3622406A (en)

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US71063168A 1968-03-05 1968-03-05

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BE (1) BE726565A (es)
FR (1) FR1600154A (es)

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2543893A1 (de) * 1974-10-02 1976-04-08 Nat Distillers Chem Corp Verfahren zur herstellung eines warmgeformten produktes aus titan
US4075070A (en) * 1976-06-09 1978-02-21 Ppg Industries, Inc. Electrode material
US4092614A (en) * 1974-09-21 1978-05-30 Nippon Electric Co., Ltd. Semiconductor laser device equipped with a silicon heat sink
US4129438A (en) * 1976-03-23 1978-12-12 Rmi Company Method of adding trace elements to base metals
US4512826A (en) * 1983-10-03 1985-04-23 Northeastern University Precipitate hardened titanium alloy composition and method of manufacture
JPS60251239A (ja) * 1984-05-25 1985-12-11 Daido Steel Co Ltd 快削チタン合金およびその製造方法
US4576660A (en) * 1985-02-15 1986-03-18 General Electric Company Oxysulfide dispersion strengthened titanium compositions
US4578129A (en) * 1985-02-15 1986-03-25 General Electric Company Oxysulfide dispersion strengthened titanium alloys
US4639281A (en) * 1982-02-19 1987-01-27 Mcdonnell Douglas Corporation Advanced titanium composite
US4906436A (en) * 1988-06-27 1990-03-06 General Electric Company High strength oxidation resistant alpha titanium alloy
US5238883A (en) * 1989-01-13 1993-08-24 Lanxide Technology Company, Lp Process for preparing self-supporting bodies and products produced thereby
US5830288A (en) * 1994-09-26 1998-11-03 General Electric Company Titanium alloys having refined dispersoids and method of making
US6685882B2 (en) 2001-01-11 2004-02-03 Chrysalis Technologies Incorporated Iron-cobalt-vanadium alloy
US20060102255A1 (en) * 2004-11-12 2006-05-18 General Electric Company Article having a dispersion of ultrafine titanium boride particles in a titanium-base matrix
WO2005060631A3 (en) * 2003-12-11 2007-05-31 Univ Ohio Titanium alloy microstructural refinement method and high temperature, high strain rate superplastic forming of titanium alloys
US10100386B2 (en) 2002-06-14 2018-10-16 General Electric Company Method for preparing a metallic article having an other additive constituent, without any melting
US10570469B2 (en) 2013-02-26 2020-02-25 Ati Properties Llc Methods for processing alloys
US10619226B2 (en) * 2015-01-12 2020-04-14 Ati Properties Llc Titanium alloy
US11111552B2 (en) 2013-11-12 2021-09-07 Ati Properties Llc Methods for processing metal alloys
US11136650B2 (en) * 2016-07-26 2021-10-05 The Boeing Company Powdered titanium alloy composition and article formed therefrom

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2567153B1 (fr) * 1984-07-06 1991-04-12 Onera (Off Nat Aerospatiale) Procede d'elaboration, par metallurgie des poudres, d'alliage a base de titane a faible dimension de grain
EP0192953A1 (en) * 1985-02-15 1986-09-03 General Electric Company Oxysulfide dispersion strengthened titanium alloys
EP0199198A1 (en) * 1985-04-12 1986-10-29 Daido Tokushuko Kabushiki Kaisha Free-cutting ti alloy
DE69128692T2 (de) * 1990-11-09 1998-06-18 Toyoda Chuo Kenkyusho Kk Titanlegierung aus Sinterpulver und Verfahren zu deren Herstellung

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB726203A (en) * 1953-01-06 1955-03-16 Magnesium Elektron Ltd Improvements in or relating to titanium alloys
US2797996A (en) * 1953-12-07 1957-07-02 Rem Cru Titanium Inc Titanium base alloys
CA594813A (en) * 1960-03-22 I. Jaffee Robert Zirconium-containing alpha dispersoid titanium base alloys
US3052538A (en) * 1960-04-21 1962-09-04 Robert W Jech Titanium base alloys
US3199980A (en) * 1961-09-04 1965-08-10 Nat Res Dev Titanium alloys
US3340051A (en) * 1963-10-02 1967-09-05 Imp Metal Ind Kynoch Ltd Titanium-base alloys
US3379522A (en) * 1966-06-20 1968-04-23 Titanium Metals Corp Dispersoid titanium and titaniumbase alloys

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA594813A (en) * 1960-03-22 I. Jaffee Robert Zirconium-containing alpha dispersoid titanium base alloys
GB726203A (en) * 1953-01-06 1955-03-16 Magnesium Elektron Ltd Improvements in or relating to titanium alloys
US2797996A (en) * 1953-12-07 1957-07-02 Rem Cru Titanium Inc Titanium base alloys
US3052538A (en) * 1960-04-21 1962-09-04 Robert W Jech Titanium base alloys
US3199980A (en) * 1961-09-04 1965-08-10 Nat Res Dev Titanium alloys
US3340051A (en) * 1963-10-02 1967-09-05 Imp Metal Ind Kynoch Ltd Titanium-base alloys
US3379522A (en) * 1966-06-20 1968-04-23 Titanium Metals Corp Dispersoid titanium and titaniumbase alloys

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Titanium Abstracts Bulletin, Vol. 4, Imperical Chemical Ind. Limited, July 1958 June 1959, pg. 122 *

Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4092614A (en) * 1974-09-21 1978-05-30 Nippon Electric Co., Ltd. Semiconductor laser device equipped with a silicon heat sink
US3963525A (en) * 1974-10-02 1976-06-15 Rmi Company Method of producing a hot-worked titanium product
DE2543893A1 (de) * 1974-10-02 1976-04-08 Nat Distillers Chem Corp Verfahren zur herstellung eines warmgeformten produktes aus titan
US4129438A (en) * 1976-03-23 1978-12-12 Rmi Company Method of adding trace elements to base metals
US4075070A (en) * 1976-06-09 1978-02-21 Ppg Industries, Inc. Electrode material
US4133730A (en) * 1976-06-09 1979-01-09 Ppg Industries, Inc. Electrolysis of brine using titanium alloy electrode
US4639281A (en) * 1982-02-19 1987-01-27 Mcdonnell Douglas Corporation Advanced titanium composite
US4512826A (en) * 1983-10-03 1985-04-23 Northeastern University Precipitate hardened titanium alloy composition and method of manufacture
JPS60251239A (ja) * 1984-05-25 1985-12-11 Daido Steel Co Ltd 快削チタン合金およびその製造方法
JPH0542490B2 (es) * 1984-05-25 1993-06-28 Daido Steel Co Ltd
US4576660A (en) * 1985-02-15 1986-03-18 General Electric Company Oxysulfide dispersion strengthened titanium compositions
US4578129A (en) * 1985-02-15 1986-03-25 General Electric Company Oxysulfide dispersion strengthened titanium alloys
US4906436A (en) * 1988-06-27 1990-03-06 General Electric Company High strength oxidation resistant alpha titanium alloy
US5238883A (en) * 1989-01-13 1993-08-24 Lanxide Technology Company, Lp Process for preparing self-supporting bodies and products produced thereby
US5830288A (en) * 1994-09-26 1998-11-03 General Electric Company Titanium alloys having refined dispersoids and method of making
US20040089377A1 (en) * 2001-01-11 2004-05-13 Deevi Seetharama C. High-strength high-temperature creep-resistant iron-cobalt alloys for soft magnetic applications
US7776259B2 (en) 2001-01-11 2010-08-17 Philip Morris Usa Inc. High-strength high-temperature creep-resistant iron-cobalt alloys for soft magnetic applications
US6946097B2 (en) 2001-01-11 2005-09-20 Philip Morris Usa Inc. High-strength high-temperature creep-resistant iron-cobalt alloys for soft magnetic applications
US20070289676A1 (en) * 2001-01-11 2007-12-20 Philip Morris Usa Inc. High-strength high-temperature creep-resistant iron-cobalt alloys for soft magnetic applications
US6685882B2 (en) 2001-01-11 2004-02-03 Chrysalis Technologies Incorporated Iron-cobalt-vanadium alloy
US10100386B2 (en) 2002-06-14 2018-10-16 General Electric Company Method for preparing a metallic article having an other additive constituent, without any melting
WO2005060631A3 (en) * 2003-12-11 2007-05-31 Univ Ohio Titanium alloy microstructural refinement method and high temperature, high strain rate superplastic forming of titanium alloys
US8562714B2 (en) 2004-11-12 2013-10-22 General Electric Company Article having a dispersion of ultrafine titanium boride particles in a titanium-base matrix
US20090229411A1 (en) * 2004-11-12 2009-09-17 General Electric Company Article having a dispersion of ultrafine titanium boride particles in a titanium-base matrix
US7531021B2 (en) * 2004-11-12 2009-05-12 General Electric Company Article having a dispersion of ultrafine titanium boride particles in a titanium-base matrix
US20060102255A1 (en) * 2004-11-12 2006-05-18 General Electric Company Article having a dispersion of ultrafine titanium boride particles in a titanium-base matrix
US10604452B2 (en) 2004-11-12 2020-03-31 General Electric Company Article having a dispersion of ultrafine titanium boride particles in a titanium-base matrix
US10570469B2 (en) 2013-02-26 2020-02-25 Ati Properties Llc Methods for processing alloys
US11111552B2 (en) 2013-11-12 2021-09-07 Ati Properties Llc Methods for processing metal alloys
US10619226B2 (en) * 2015-01-12 2020-04-14 Ati Properties Llc Titanium alloy
US10808298B2 (en) 2015-01-12 2020-10-20 Ati Properties Llc Titanium alloy
US11319616B2 (en) 2015-01-12 2022-05-03 Ati Properties Llc Titanium alloy
US11851734B2 (en) 2015-01-12 2023-12-26 Ati Properties Llc Titanium alloy
US11136650B2 (en) * 2016-07-26 2021-10-05 The Boeing Company Powdered titanium alloy composition and article formed therefrom

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BE726565A (es) 1969-06-16
FR1600154A (es) 1970-07-20

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