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US20060105194A1 - Defect healing of deposited titanium alloys - Google Patents

Defect healing of deposited titanium alloys Download PDF

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Publication number
US20060105194A1
US20060105194A1 US10/991,604 US99160404A US2006105194A1 US 20060105194 A1 US20060105194 A1 US 20060105194A1 US 99160404 A US99160404 A US 99160404A US 2006105194 A1 US2006105194 A1 US 2006105194A1
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US
United States
Prior art keywords
heating
transus
temperature
equilibrium
essentially
Prior art date
Legal status (The legal status 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 status listed.)
Abandoned
Application number
US10/991,604
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English (en)
Inventor
Monika Kinstler
Orest Ivasishin
Pavel Markovsky
Vadim Bondarchuk
Gregory Serhiyenko
Igor Belousov
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RTX Corp
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Individual
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
Priority to US10/991,604 priority Critical patent/US20060105194A1/en
Application filed by Individual filed Critical Individual
Assigned to UNITED TECHNOLOGIES CORPORATION reassignment UNITED TECHNOLOGIES CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BELOUSOV, IGOR V., BONDARCHUK, VADIM I., IVASISHIN, OREST M., MARKOVSKY, PAVEL E., SERHIYENKO, GREGORY A., KINSTLER, MONIKA D.
Priority to DE602005008169T priority patent/DE602005008169D1/de
Priority to EP05255509A priority patent/EP1662019B1/en
Priority to AT05255509T priority patent/ATE401429T1/de
Priority to UAA200509015A priority patent/UA79864C2/uk
Priority to SG200508453A priority patent/SG122960A1/en
Priority to CN200510125479.2A priority patent/CN1776000A/zh
Priority to MXPA05012417A priority patent/MXPA05012417A/es
Publication of US20060105194A1 publication Critical patent/US20060105194A1/en
Assigned to RAYTHEON TECHNOLOGIES CORPORATION reassignment RAYTHEON TECHNOLOGIES CORPORATION CHANGE OF NAME Assignors: UNITED TECHNOLOGIES CORPORATION
Assigned to RAYTHEON TECHNOLOGIES CORPORATION reassignment RAYTHEON TECHNOLOGIES CORPORATION CORRECTIVE ASSIGNMENT TO CORRECT THE AND REMOVE PATENT APPLICATION NUMBER 11886281 AND ADD PATENT APPLICATION NUMBER 14846874. TO CORRECT THE RECEIVING PARTY ADDRESS PREVIOUSLY RECORDED AT REEL: 054062 FRAME: 0001. ASSIGNOR(S) HEREBY CONFIRMS THE CHANGE OF ADDRESS. Assignors: UNITED TECHNOLOGIES CORPORATION
Assigned to RTX CORPORATION reassignment RTX CORPORATION CHANGE OF NAME Assignors: RAYTHEON TECHNOLOGIES CORPORATION
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • 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

Definitions

  • the invention relates to deposition of Ti-based materials. More particularly, the invention relates to addressing deposition defects.
  • EBPVD electron beam physical vapor deposition
  • Such techniques may be used in the aerospace industry for the repair or remanufacture of damaged or worn parts such as gas turbine engine components (e.g., blades, vanes, seals, and the like).
  • Deposition defects potentially compromise the condensate integrity.
  • One group of such defects arises when a droplet of material is spattered onto the substrate or the accumulating condensate.
  • the melt pool may contain additives not intended to vaporize and accumulate in the condensate.
  • U.S. Pat. No. 5,474,809 discloses use of refractory elements in the melt pool.
  • One aspect of the invention involves a method for treating a deposited titanium-base material from an initial condition to a treated condition.
  • the material is heated from a first temperature to a second temperature.
  • the first temperature is below an equilibrium ⁇ transus.
  • the second temperature is above the equilibrium ⁇ transus.
  • the heating includes a portion at a rate in excess of 5° C./s.
  • the material is cooled from the second temperature to a third temperature below the equilibrium ⁇ transus.
  • the heating may be to a peak at least 10° C. above a non-equilibrium ⁇ transus.
  • the material may be above the equilibrium ⁇ transus for a brief period (e.g., no more than 2.0 seconds).
  • the heating and cooling may have sufficient rates to maintain a characteristic grain size of at least a matrix of the material below 100 ⁇ m.
  • the material may include a number of defects having trunks with microstructures distinct from a microstructure of a matrix of the material.
  • the trunks' microstructures may be essentially integrated with the matrix microstructure.
  • the heating may be to a peak 10-50° C. above a non-equilibrium ⁇ transus.
  • the material may be above the equilibrium ⁇ transus for a very brief period (e.g., no more than 1.0 seconds).
  • the heating may be to 1-30° C. above the equilibrium ⁇ transus for a somewhat longer period (e.g., 1.0-5.0 seconds).
  • the cooling may be sufficiently rapid to limit ⁇ growth to a characteristic size smaller than 100 ⁇ m.
  • One group of materials consist in largest weight parts of titanium, aluminum, and vanadium.
  • An exemplary material thickness may be at least 2.0 mm (e.g., for relatively thick structural and repair material, contrasted with thinner coatings).
  • FIG. 1 is an optical micrograph of a Ti-6Al-4V condensate atop a like substrate and showing defects.
  • FIG. 2 is a view of a healed condensate.
  • FIG. 3 is a temperature-time diagram showing healing processes.
  • FIG. 1 shows a condensate 20 accumulated atop a surface 22 of a substrate 24 .
  • Exemplary condensate thickness may be from less than 0.2 ⁇ mm (e.g., for thin coatings) to in excess of 2 mm (at least locally—e.g., for structural condensates such as certain repairs).
  • the condensate has a first defect 26 triggered by a spattered molybdenum droplet 28 that landed atop the surface 22 .
  • Exemplary droplet sizes are 30-500 ⁇ m (measured as a characteristic (mean/median/mode) transverse dimension).
  • the defect comprises a trunk 30 extending from the droplet 28 toward the condensate surface (not shown).
  • a second defect 32 is shown and may have been triggered by a droplet below the cut surface of the view.
  • the exemplary deposition is of nominal Ti-6Al-4V condensate atop a like substrate.
  • Alternate depositions may include Ti-6Al-2Sn-4Zr-2Mo and Ti-8Al-1Mo-1V.
  • the deposition may be from a melted ingot at least partially through a pool containing one or more refractory or other elements which may be essentially non-consumed during deposition (e.g., a pool formed from a 30%Mo-70%Zr mixture). Accordingly, the droplets may tend to have composition similar to the surface layers of the pool. In the absence of the non-consumed pool additive, the droplet 28 might have a similar composition to the ingot yet still produce similar defects. Many droplets in systems using an Mo-containing pool would have Mo concentrations of at least 10% by weight; others at least 20%. This may be somewhat less than the Mo percentage of the non-expending pool material to reflect possible dilution by deposition material elements in the pool.
  • the substrate 28 has an ⁇ - ⁇ microstructure of medium to coarse grains (e.g., 10-40 ⁇ m characteristic grain size (e.g., mean) or about ASTM 10.5-6.5).
  • An exemplary 10-20% by weight of the substrate is ⁇ phase with the remainder essentially a phase.
  • the condensate matrix (away from the defects) also has an ⁇ - ⁇ microstructure but of very fine grains (e.g., acicular ⁇ grains of 5-10 m in length and 2-5 ⁇ m in thickness, lengthwise oriented along the condensate growth/deposition direction).
  • the trunk size will depend, in substantial part, upon the droplet size. Exemplary trunk diameters are from about 20 ⁇ m to about 50 ⁇ m. However, much larger trunks are possible.
  • the trunks have a columnar ⁇ - ⁇ microstructure.
  • This microstructure may have a characteristic grain size several times greater than that in the matrix and the grains may be elongated in the direction of accumulation (i.e., away from the substrate).
  • the grain discontinuity at the trunk-matrix interface and the particular alignment of trunk grains may cause structural weaknesses affecting, inter alia, ductility, fracture toughness, fatigue resistance, fretting fatigue resistance, corrosion resistance, wear resistance, crack nucleation resistance, and the like.
  • FIG. 2 shows a condensate 50 after healing.
  • the substrate is not shown.
  • the condensate surface 52 is, however, shown.
  • a defect within the condensate had been caused by a droplet 54 .
  • the resultant trunk had propagated all the way to the surface forming a bulge 56 .
  • the healed condensate shows essentially no remaining artifacts of the defect other than the original droplet 54 and bulge 56 .
  • the trunk has been microstructurally integrated with the condensate matrix as a fine ⁇ equiaxed microstructure (e.g., grain size of 10-100 ⁇ m ( ⁇ ASTM 10.5-3.5)).
  • laminar variations in chemistry or microstructure may be diminished or eliminated, thereby increasing the isotropy of the condensate mechanical properties.
  • the bulge 56 may be removed (e.g., during a subsequent surface machining).
  • the healing permits the workpiece (e.g., a blade, vane, seal, or the like) to be operated at ambient temperature (e.g., 0-40° C.) and/or at elevated temperatures (e.g., above 250° C., such as in the range of 300-500° C.) essentially without increased chances of failure.
  • the workpiece is initially at room temperature (condition/location 100 ) on the temperature against time plot of FIG. 3 .
  • FIG. 3 further shows a line 102 representing the equilibrium ⁇ transus (T e ⁇ ) as well as curves 104 and 106 of non-equilibrium ⁇ transus temperatures for the condensate and substrate, respectively (specific to the microstructural and thermal history of this Example 1).
  • the equilibrium ⁇ transus temperature is a function of chemistry only. Because the exemplary condensate and substrate have the same chemistry, they share the same equilibrium ⁇ transus temperature (e.g., 960-1010° C. for Ti-6Al-4V).
  • the non-equilibrium ⁇ transus temperature is a function of composition, grain size/morphology, and heating rate. The smaller the grains, the lower the transus temperature. The more rapid the heating rate, the higher the transus temperature. At very slow heating rates, the equilibrium transus temperature equals the non-equilibrium transus temperature. Given very fine condensate grains, medium to coarse substrate grains, and a heating rate of approximately 100° C./sec, it is estimated that the difference between the non-equilibrium ⁇ transus of the two structures is about 100° C.
  • the workpiece is heated 109 moderately above the condensate non-equilibrium ⁇ transus (condition/location 110 ).
  • This heating may be under vacuum or in an inert atmosphere.
  • This heating is advantageously rapid (e.g., occurring at a rate of 5-100° C./s or greater) so as to prevent excessive grain growth.
  • Excessive grain growth e.g., above 150 ⁇ m ( ⁇ ASTM 2.5) or even 100 ⁇ m ( ⁇ ASTM 3.5), depending upon the application) is disadvantageous because it excessively reduces structural properties including one or more of ductility, fracture toughness, fatigue resistance, fretting fatigue resistance, corrosion resistance, wear resistance, crack nucleation resistance, and the like.
  • the heating reaches a peak of ⁇ T 1 above the condensate non-equilibrium ⁇ transus of approximately 10-50° C.
  • the heating substantially converts the condensate microstructure to ⁇ .
  • the upper limit on ⁇ T 1 will reflect the microstructural/thermal history and is advantageously sufficiently low to avoid excessive ⁇ grain growth (in view of time considerations discussed below).
  • the lower limit is advantageously high enough to provide essentially complete transition to the ⁇ phase ( ⁇ + ⁇ to ⁇ ).
  • the substrate may be essentially unaffected.
  • the workpiece is rapidly cooled 111 back to room temperature (condition/location 112 ).
  • This heating may be under the same vacuum or atmosphere as the first stage.
  • metastable martensite may accumulate in the condensate and the substrate.
  • the cooling is advantageously sufficiently rapid to further limit ⁇ (grain growth.
  • the rapid heating and cooling maintain the condensate above its equilibrium ⁇ transus for a time interval sufficiently brief to avoid the excessive ⁇ grain growth noted above while providing the ⁇ phase transition.
  • An exemplary time interval above the equilibrium ⁇ transus is 1.0 seconds or less.
  • This microstructure is characterized by preservation of the boundaries of the prior ⁇ grains with a (e.g., in needle- or platelet-like form) in a ⁇ matrix within such boundaries.
  • the rapid heating and cooling may provide a sufficiently short time at elevated temperature (in view of the magnitude of such temperature) to greatly limit oxidation even if the procedure is performed in an ambient atmosphere rather than under vacuum or an inert atmosphere.
  • elevated temperature in view of the magnitude of such temperature
  • An optional third stage involves annealing/aging by heating the workpiece to an annealing temperature (e.g., in the vicinity of 500-600° C. for the exemplary Ti alloy).
  • the exemplary annealing/aging is for a period of 1-24 hours and is effective to eliminate the martensite but without producing ⁇ grain growth. This may leave the condensate as essentially fine grain ⁇ (e.g., broadly smaller than 150 ⁇ m, more narrowly smaller than 100 ⁇ m, and preferably smaller than 50 ⁇ m ( ⁇ ASTM 2.5, 3.5, and 5.5, respectively)) plus the droplets and leaves the substrate as essentially medium to coarse grain ⁇ - ⁇ .
  • the cooling of the second stage may be sufficiently slow to avoid martensite formation, in which case it is particularly appropriate to omit the aging/annealing.
  • the initial heating stage 119 is similarly rapid but to a temperature above the equilibrium ⁇ transus but below the condensate non-equilibrium ⁇ transus.
  • the resulting condition/location 120 may be at a temperature of ⁇ T 2 above the equilibrium ⁇ transus (e.g., by 10-30° C.).
  • the upper limit on this range is advantageously effective to avoid excessive ⁇ grain growth.
  • the lower limit on this range is advantageously high enough to provide essentially complete transition to the ⁇ phase ( ⁇ + ⁇ to ⁇ ).
  • the substrate may be essentially unaffected.
  • the workpiece is maintained 121 at such a temperature for a moderate time interval (e.g., of about two seconds, more broadly 1.5-4.0 seconds or 1.0-5.0 seconds) to achieve a condition/location 122 . It is during this time interval that the condensate microstructure changes to fine ⁇ as in condition/location 110 . Thereafter, a rapid cooling 123 may transition the workpiece to a condition/location 124 similar to 112 and may, in turn, be followed by a similar annealing/aging if appropriate or desired.
  • a moderate time interval e.g., of about two seconds, more broadly 1.5-4.0 seconds or 1.0-5.0 seconds
  • the heating and cooling may be performed by a variety of techniques.
  • One family of rapid heating techniques provides highly local heating (exemplary such techniques include induction heating, laser heating, electron beam heating, and the like). Such heating facilitates heating of the condensate with less substantial heating of the substrate, thereby minimizing any structural effects on the substrate.
  • the desired heating depth may be controlled in view of the coating thickness by means including frequency control of induction heating, beam intensity of laser or electron beam heating, and the like. With some implementations of such heating, the heating may progress across the condensate (e.g., by moving or reorienting the workpiece relative to the heating source). Direct electrical resistance heating may be used to more generally heat the workpiece.
  • the exemplary rapid cooling may be performed by forced cooling with an inert gas (especially when the heating is performed under vacuum), forced air cooling, liquid quench (e.g., in oil or water), and the like.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Physical Vapour Deposition (AREA)
  • Heat Treatments In General, Especially Conveying And Cooling (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Materials For Medical Uses (AREA)
  • Dental Preparations (AREA)
  • Chemically Coating (AREA)
US10/991,604 2004-11-17 2004-11-17 Defect healing of deposited titanium alloys Abandoned US20060105194A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US10/991,604 US20060105194A1 (en) 2004-11-17 2004-11-17 Defect healing of deposited titanium alloys
DE602005008169T DE602005008169D1 (de) 2004-11-17 2005-09-08 Verfahren zur Herstellung von defektfreien beschichteten Titanlegierungen
EP05255509A EP1662019B1 (en) 2004-11-17 2005-09-08 Method of producing defect free deposited titanium alloys
AT05255509T ATE401429T1 (de) 2004-11-17 2005-09-08 Verfahren zur herstellung von defektfreien beschichteten titanlegierungen
UAA200509015A UA79864C2 (en) 2004-11-17 2005-09-23 Method for treatment of sprayed titanium-based material (variants) and component
SG200508453A SG122960A1 (en) 2004-11-17 2005-11-14 Defect healing of deposited titanium alloys
MXPA05012417A MXPA05012417A (es) 2004-11-17 2005-11-17 Correccion de defectos en aleaciones de titanio depositadas.
CN200510125479.2A CN1776000A (zh) 2004-11-17 2005-11-17 沉积钛合金的缺陷修复

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US10/991,604 US20060105194A1 (en) 2004-11-17 2004-11-17 Defect healing of deposited titanium alloys

Publications (1)

Publication Number Publication Date
US20060105194A1 true US20060105194A1 (en) 2006-05-18

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Family Applications (1)

Application Number Title Priority Date Filing Date
US10/991,604 Abandoned US20060105194A1 (en) 2004-11-17 2004-11-17 Defect healing of deposited titanium alloys

Country Status (8)

Country Link
US (1) US20060105194A1 (zh)
EP (1) EP1662019B1 (zh)
CN (1) CN1776000A (zh)
AT (1) ATE401429T1 (zh)
DE (1) DE602005008169D1 (zh)
MX (1) MXPA05012417A (zh)
SG (1) SG122960A1 (zh)
UA (1) UA79864C2 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130319154A1 (en) * 2011-03-31 2013-12-05 Aisin Aw Co., Ltd. Steel gear and manufacturing method for the same
US9388476B2 (en) * 2011-03-31 2016-07-12 Aisin Aw Co., Ltd. Steel gear and manufacturing method for the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5474809A (en) * 1994-12-27 1995-12-12 General Electric Company Evaporation method
US5879760A (en) * 1992-11-05 1999-03-09 The United States Of America As Represented By The Secretary Of The Air Force Titanium aluminide articles having improved high temperature resistance
US6190473B1 (en) * 1999-08-12 2001-02-20 The Boenig Company Titanium alloy having enhanced notch toughness and method of producing same
US6626228B1 (en) * 1998-08-24 2003-09-30 General Electric Company Turbine component repair system and method of using thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5879760A (en) * 1992-11-05 1999-03-09 The United States Of America As Represented By The Secretary Of The Air Force Titanium aluminide articles having improved high temperature resistance
US5474809A (en) * 1994-12-27 1995-12-12 General Electric Company Evaporation method
US6626228B1 (en) * 1998-08-24 2003-09-30 General Electric Company Turbine component repair system and method of using thereof
US6190473B1 (en) * 1999-08-12 2001-02-20 The Boenig Company Titanium alloy having enhanced notch toughness and method of producing same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130319154A1 (en) * 2011-03-31 2013-12-05 Aisin Aw Co., Ltd. Steel gear and manufacturing method for the same
US9388476B2 (en) * 2011-03-31 2016-07-12 Aisin Aw Co., Ltd. Steel gear and manufacturing method for the same
US9441723B2 (en) * 2011-03-31 2016-09-13 Aisin Aw Co., Ltd. Steel gear and manufacturing method for the same

Also Published As

Publication number Publication date
UA79864C2 (en) 2007-07-25
MXPA05012417A (es) 2006-05-19
EP1662019B1 (en) 2008-07-16
DE602005008169D1 (de) 2008-08-28
CN1776000A (zh) 2006-05-24
SG122960A1 (en) 2006-06-29
ATE401429T1 (de) 2008-08-15
EP1662019A1 (en) 2006-05-31

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Free format text: CHANGE OF NAME;ASSIGNOR:RAYTHEON TECHNOLOGIES CORPORATION;REEL/FRAME:064402/0837

Effective date: 20230714