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US20100230017A1 - Ultra-High Strength, Corrosion Resistant Wire, a Method of Making Same, and a Method of Using Same - Google Patents

Ultra-High Strength, Corrosion Resistant Wire, a Method of Making Same, and a Method of Using Same Download PDF

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Publication number
US20100230017A1
US20100230017A1 US12721844 US72184410A US20100230017A1 US 20100230017 A1 US20100230017 A1 US 20100230017A1 US 12721844 US12721844 US 12721844 US 72184410 A US72184410 A US 72184410A US 20100230017 A1 US20100230017 A1 US 20100230017A1
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passed
wire
max
step
failed
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Richard B. Frank
Lyndon W. Burleson
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Frank Richard B
Burleson Lyndon W
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    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073Shielding materials
    • H05K9/0098Shielding materials for shielding electrical cables
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/02Layer formed of wires, e.g. mesh
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • C22C19/05Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/055Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • C22C19/05Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/056Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/07Alloys based on nickel or cobalt based on cobalt
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C30/00Alloys containing less than 50% by weight of each constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2922Nonlinear [e.g., crimped, coiled, etc.]
    • Y10T428/2925Helical or coiled

Abstract

A method of making steel wire is described that includes the step of forming a length of wire from a high strength, corrosion resistant alloy. The alloy preferably has the following composition in weight percent.
Carbon 0.03 max. Manganese 0.15 max. Silicon 0.15 max. Phosphorus 0.015 max. Sulfur 0.010 max. Chromium 19.00-21.00 Nickel 33.00-37.00 Molybdenum  9.00-10.50 Titanium 1.00 max. Boron 0.010 max. Iron 1.00 max.
The balance of the alloy is cobalt and usual impurities. The wire is annealed at a combination of temperature and time effective to provide a grain size of about ASTM 6 or finer. The annealed wire is then drawn such that the cross-sectional area of the wire is reduced by about 50 to 80%. The as-drawn wire is then heat treated at a second combination of temperature and time effective to provide the wire with high strength and sufficient ductility that when the wire is wrapped to provide a coil having an inside diameter substantially commensurate with the diameter of the wire and then unwrapped it does not crack or break.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • [0001]
    This application claims the benefit of U.S. Provisional Application No. 61/159,577, filed Mar. 12, 2009, the entirety of which is incorporated herein by reference.
  • BACKGROUND OF THE INVENTION
  • [0002]
    1. Field of the Invention
  • [0003]
    This invention generally relates to fine gauge, high strength wire, and in particular, it relates to a wire product that provides a unique combination of very high strength, excellent ductility, and good corrosion resistance for use in armored cable.
  • [0004]
    2. Description of the Related Art
  • [0005]
    Armored communication cable has been used for transmission of communication and control signals to equipment operating in oil wells, particularly in deep sour gas wells. One type of armored cable for the oil well application is described in U.S. Pat. No. 6,255,592, the entire disclosure of which is incorporated herein by reference. Typically, the armor portion of such cables is made from steel wire that contains a medium to high amount of carbon. It is also known to use stainless steel wire for the armoring portion of armored cable used in oil wells. The wire used for making armored cable sheath is typically used at a tensile strength level of 275-295 ksi. However, the users of such cables are now demanding even higher strength levels for this application.
  • [0006]
    The alloy designated UNS R00035 is a corrosion resistant Ni—Co base alloy that provides a tensile strength of up to about 300 ksi. At least one specification for cable armor requires the use of the UNS R00035 alloy. However, when that alloy is processed to produce wire having a tensile strength in excess of 300 ksi, the alloy lacks sufficient ductility to resist breaking in a standard wire-wrap test. Accordingly, it would be advantageous to produce a corrosion resistant Ni—Co base alloy wire that can be processed to wire form, that provides a tensile strength in excess of 300 ksi, and which also provides sufficient ductility to meet the wire-wrap test.
  • SUMMARY OF THE INVENTION
  • [0007]
    In accordance with a first aspect of the present invention there is provided a method of making steel wire. The method according to this invention includes the step of forming a length of wire from a high strength, corrosion resistant alloy. The alloy preferably has the following composition in weight percent.
  • [0000]
    Carbon 0.03 max.
    Manganese 0.15 max.
    Silicon 0.15 max.
    Phosphorus 0.015 max.
    Sulfur 0.010 max.
    Chromium 19.00-21.00
    Nickel 33.00-37.00
    Molybdenum  9.00-10.50
    Titanium 1.00 max.
    Boron 0.010 max.
    Iron 1.00 max.

    The balance of the alloy is cobalt and usual impurities. The wire is annealed at a combination of temperature and time effective to provide a grain size of about ASTM 6 or finer. The annealed wire is then drawn such that the cross-sectional area of the wire is reduced by about 50 to 80%. The as-drawn wire is then heat treated at a second combination of temperature and time effective to provide the wire with high strength and sufficient ductility that when the wire is wrapped to provide a coil having an inside diameter substantially commensurate with the diameter of the wire and then unwrapped, the wire does not crack or break.
  • [0008]
    In accordance with another aspect of the present invention there is provided a method of making flexible armored cable. This method includes the step of forming a length of wire from an alloy comprising, in weight percent, about
  • [0000]
    Carbon 0.03 max.
    Manganese 0.15 max.
    Silicon 0.15 max.
    Phosphorus 0.015 max.
    Sulfur 0.010 max.
    Chromium 19.00-21.00
    Nickel 33.00-37.00
    Molybdenum  9.00-10.50
    Titanium 1.00 max.
    Boron 0.010 max.
    Iron 1.00 max.

    The balance of the alloy is cobalt and the usual impurities. The wire is then annealed at a combination of temperature and time effective to provide a grain size of about ASTM 6 or finer. The annealed wire is then drawn such that the cross-sectional area of the wire is reduced by about 50 to 80%. The wire is then heat treated at a second combination of temperature and time that is effective to provide the alloy with high strength and sufficient ductility that when the wire is wrapped to provide a coil having an inside diameter substantially commensurate with the diameter of the wire and then unwrapped, the wire does not crack or break. The heat treated wire is then helically wound around an elongated core member to form a flexible encasement around the elongated core member.
  • [0009]
    In accordance with a further aspect of the present invention, there is provided a wire formed from a high strength, corrosion resistant alloy having the following composition in weight percent, about
  • [0000]
    Carbon 0.03 max.
    Manganese 0.15 max.
    Silicon 0.15 max.
    Phosphorus 0.015 max.
    Sulfur 0.010 max.
    Chromium 19.00-21.00
    Nickel 33.00-37.00
    Molybdenum  9.00-10.50
    Titanium 1.00 max.
    Boron 0.010 max.
    Iron 1.00 max.

    The balance of the alloy is cobalt and the usual impurities. The wire is characterized by a tensile strength in excess of 300 ksi and sufficient ductility that when the wire is wrapped to provide a coil having an inside diameter substantially equal to the diameter of the wire and then unwrapped, the wire does not crack or break.
  • [0010]
    Here and throughout this specification the following definitions apply unless otherwise indicated. The term “percent” and the symbol “%” are used in expressing weight percent, mass percent, or percent reduction in cross-sectional area, except as otherwise indicated. ASTM grain size numbers are those determined in accordance with ASTM Standard E112-96 (2004), “Standard Test Methods for Determining Average Grain Size” (DOI: 10.1520/E0112-96R04).
  • BRIEF DESCRIPTION OF THE DRAWING
  • [0011]
    The drawing FIGURE is a chart that shows the effects of cold working and aging temperature on the ultimate tensile strength and wrap test performance of high strength wire.
  • DETAILED DESCRIPTION
  • [0012]
    In accordance with the present invention, the known composition and the known processing of UNS R00035 alloy are modified to provide a wire product having a novel combination of tensile strength and ductility as well as good corrosion resistance. In accordance with the first step in the process according to this invention, an alloy having the following weight percent composition is melted, refined, and cast into an ingot mold.
  • [0000]
    Carbon 0.03 max.
    Manganese 0.15 max.
    Silicon 0.15 max.
    Phosphorus 0.015 max.
    Sulfur 0.010 max.
    Chromium 19.00-21.00
    Nickel 33.00-37.00
    Molybdenum  9.00-10.50
    Titanium 1.00 max.
    Boron 0.010 max.
    Iron 1.00 max.
    Cobalt + Impurities Balance

    The ingot is removed from the mold upon solidification and then mechanically worked into intermediate product forms having progressively smaller cross sections. Processes for melting, casting, and mechanically working the alloy are known and described in U.S. Pat. No. 3,356,542 and U.S. Pat. No. 3,562,042, the entire disclosures of which are incorporated herein by reference. It is believed that a low Ti grade of this alloy, i.e., 0.01% max. Ti, will also provide acceptable results.
  • [0013]
    The process according to this invention is designed to produce a wire product from the alloy which has a fine, recrystallized grain structure prior to cold drawing. Commercial specifications for the UNS R00035 alloy, such as AMS 5844 which relates to bar products, require an annealing treatment at 1900-1925° F. for 4 to 8 hours. That annealing heat treatment provides a medium grain size in the range of ASTM 4 to 6. We have discovered that a lower annealing temperature, preferably about 1750-1850° F. provides a finer grain size (ASTM 6 or finer) which is believed to result in a better combination of strength and ductility even when the alloy is in the cold-worked condition. The annealing step is preferably carried out for about 0.5 to 2 hours. After solution annealing, the alloy is heavily cold drawn in the range of about 50-80% reduction in cross-sectional area (R.C.S.A.), preferably about 65-75% R.C.S.A. to obtain a tensile strength exceeding about 300 ksi. Typically, armoring cable products are then used in the as-cold-drawn condition. Another aspect of this invention is to age-harden the alloy wire at a temperature of 900-1400° F. to improve the overall combination of strength and ductility. In the age-hardened condition, the alloy provides an ultimate tensile strength of at least about 310 ksi together with excellent ductility as demonstrated by the wire's resistance to breaking in the wrap test. Furthermore, it is also believed that overaging the wire at a temperature greater than 1100° F. provides better ductility than the standard aging temperature of 1000-1050° F.
  • [0014]
    The processing steps used to obtain the desired combination of strength and bendability do not appear to adversely affect the corrosion resistance provided by the alloy used to make wire products in accordance with this invention. However, it is believed that the corrosion resistance of the wire product is affected by the cleanliness of the wire surface after processing. Therefore, the annealing and aging heat treatments of the wire are preferably carried out under a subatmospheric pressure to substantially avoid oxidation or other contamination of the wire surface. A subatmospheric pressure of less than about 1 torr (130 Pa) is preferred.
  • WORKING EXAMPLES Example 1
  • [0015]
    Experimental trials were performed using 0.0565 in rd. wire from a triple melted heat having the weight percent composition set forth in Table I below. Triple melting is a known technique that includes the steps of vacuum induction melting (VIM), followed by electroslag remelting (ESR), and then vacuum arc remelting (VAR). The wire was annealed at subatmospheric pressure at 1800° F. for 90 minutes and then quenched in argon gas. The grain size of the annealed wire was about ASTM size 6-8. Wire samples cut from the annealed coils were cold drawn to 50%, 55%, 60%, 64%, and 67% reductions in cross-sectional area (R.C.S.A.) to provide wire diameters of 0.040 in., 0.038 in., 0.036 in., 0.034 in., and 0.032 in., respectively. Cold drawing is performed with the wire at room (ambient) temperature. The wire samples were then aged at temperatures in the range of 1050° F.-1250° F. in argon-filled SEN/PAK® heat treating containers. Fine wire tensile tests and wrap tests were conducted to determine the strength and ductility of the wire. The wrap test consists of wrapping the wire around its own circumference five times followed by unwrapping. The test sample passes if the wire does not crack or break during wrapping or unwrapping.
  • [0000]
    TABLE I
    Element Example 1 Example 2
    C 0.010 0.008
    Mn 0.01 0.01
    Si 0.03 0.03
    P 0.002 <0.001
    S 0.002 0.002
    Cr 20.75 20.57
    Ni 34.76 34.75
    Mo 9.53 9.52
    Co 33.36 33.86
    Cb 0.03 0.06
    Al 0.12
    Ti 0.81 0.76
    B 0.0096 0.0106
    Fe 0.50 0.45
    O <10 ppm
    N  41 ppm 41 ppm
  • [0016]
    Initial results were promising for the greatest cold reduction used (67%) and for the higher aging temperatures. Additional testing was conducted using R.C.S.A.'s of 69%, 73%, and 78% and aging temperatures up to 1350° F. Tables II and III below show the results of the room temperature tensile and wrap tests for the cold-drawn and aged fine wire samples including the 0.2% offset yield strength (0.2% Y.S.) and the ultimate tensile strength (U.T.S.) in ksi, the percent elongation (% El.), and the reduction in cross-sectional area (% R.A.). It should be noted that the tensile ductility values are approximate because of the difficulty in measuring the percent elongation and percent reduction in area of fine wire samples.
  • [0000]
    TABLE II
    Wire % Cold Aging 0.2%
    Diameter Drawn Treatment Y.S. U.T.S. % El. % R.A. Wrap Test
    0.0565 in.  0 None 66 156 50 54 passed
    0 67 157 48 54
    0 68 159 48 54
    0.040 in. 50 None 207 268 5 passed
    50 214 269 5
    50 215 268 5
    50 1050° F./4 h/AC 313 323 3 67 passed
    50 305 317 3 67 passed
    50 313 323 3 67
    50 1150° F./4 h/AC 305 309 1 40 passed
    50 306 308 1 40 passed
    50 305 307 1 32 passed
    50 1250° F./4 h/AC 279 286 1 32 passed
    50 287 290 1 36 passed
    50 288 292 1 44 passed
    0.038 in. 55 None 200 279 3 60 passed
    55 196 279 3 60
    55 198 279 3 60
    55 1050° F./4 h/AC 317 331 2 45 failed
    55 327 340 2 45 failed
    55 322 336 2 45
    55 1150° F./4 h/AC 279 325 1 37 passed
    55 285 327 1 41 passed
    55 300 327 1 41 passed
    55 1250° F./4 h/AC 286 301 1 41 passed
    55 293 309 1 41 passed
    55 308 312 1 37 passed
    0.036 in. 60 None 225 282 4 passed
    60 222 280 4 passed
    60 225 281 4
    60 1050° F./4 h/AC 315 344 2 59 failed
    passed on retest
    60 326 345 2 63 passed
    60 325 342 2 56
    60 1150° F./4 h/AC 329 334 1 36 passed
    60 315 328 1 36 passed
    60 311 327 1 32 passed
    60 1250° F./4 h/AC 317 322 1 45 passed
    60 307 307 1 50 passed
    60 307 316 1 54 passed
    60 322 333 2 45 passed
    60 311 329 2 49
    60 331 338 2 31
    0.034 in. 64 None 244 295 4 57 passed
    64 252 299 4 57
    64 246 295 4 57
    64 1050° F./4 h/AC 348 360 2 49 did not wrap
    64 343 359 2 50 failed
    64 349 360 2 50
    64 1150° F./4 h/AC 302 339 2 50 failed
    64 307 341 1 45 passed
    64 306 345 1 45 passed
    64 1250° F./4 h/AC 312 318 2 49 passed
    64 311 317 2 53
    64 304 311 2 49
    64 1250° F./4 h/AC 331 335 2 26 passed
    64 324 328 1 21 passed
    64 324 331 1 26 passed
    64 1300° F./4 h/AC 325 326 1 26 passed
    64 328 331 1 31 passed
    64 316 320 1 31 passed
  • [0000]
    TABLE III
    Wire % Cold Aging 0.2%
    Diameter Drawn Treatment Y.S. U.T.S. % El. % R.A. Wrap Test
    0.0325 in. 67 None 273 299 3 passed
    67 264 304 4
    67 274 306 3
    67 1050° F./4 h/AC 337 358 2 58 did not wrap
    67 340 359 2 54 failed
    67 335 360 2 58
    67 1150° F./4 h/AC 346 354 1 50 failed
    67 348 357 1 46 failed
    67 356 358 1 46 failed
    67 1200° F./4 h/AC 338 358 1 41 failed
    67 351 358 1 46 failed
    67 338 346 1 41 failed
    67 1250° F./4 h/AC 325 342 3 40 passed
    67 330 343 2 45
    67 307 338 2 54 passed
    67 355 358 1 46 passed
    67 331 344 1 54 passed
    67 312 321 1 46 passed
    67 1275° F./4 h/AC 343 passed
    67 345 passed
    67 331 passed
    67 1300° F./4 h/AC 335 341 1 41 passed
    67 327 330 1 36 passed
    67 340 342 1 36 passed
    67 1300° F./4 h/AC 328 332 1 36 passed
    67 325 328 1 41 passed
    67 336 338 1 31 passed
    67 1350° F./4 h/AC 227 240 4 66 passed
    67 227 239 4 66
    67 226 241 4 62
    0.0316 in. 69 None 278 303 1 47 passed
    69 1250° F./4 h/AC 356 361 1 27 passed
    69 362 364 1 27 failed
    69 350 356 1 22 passed
    69 1275° F./4 h/AC 346 348 1 32 passed
    69 339 345 1 22 failed
    on unwrap
    69 348 353 1 27 passed
    69 1300° F./4 h/AC 325 337 1 32 passed
    69 321 334 1 27 passed
    69 343 347 1 33 passed
    69 1325° F./4 h/AC 329 334 2 42 passed
    69 321 328 1 37 passed
    69 315 316 2 37 passed
    69 1350° F./4 h/AC 223 235 2 47 passed
    69 257 266 2 52 passed
    69 227 238 2 51 passed
    0.0293 in. 73 None 263 306 1 44 passed
    73 1150° F./4 h/AC 207 213 1 48 failed
    73 205 207 1 49 failed
    73 203 213 1 38 failed
    73 1250° F./4 h/AC 366 370 1 38 failed
    73 362 365 1 38 passed
    73 358 366 1 38 passed
    73 1275° F./4 h/AC 328 334 1 48 pass
    73 339 341 1 43 pass
    73 325 345 1 38 failed
    on unwrap
    73 1300° F./4 h/AC 352 357 2 43 passed
    73 342 353 1 38 passed
    73 353 356 1 43 passed
    73 1325° F./4 h/AC 313 320 2 48 passed
    73 293 303 1 38 passed
    73 285 292 1 38 passed
    73 1350° F./4 h/AC 220 234 2 43 passed
    73 215 237 2 38 passed
    73 189 213 2 43 passed
    0.0263 in. 78 None 286 320 1 53 passed
    78 1250° F./4 h/AC 350 358 1 53 failed
    78 328 346 1 42 failed
    78 350 355 1 53 failed
    78 1275° F./4 h/AC 337 352 1 47 failed
    78 332 338 1 42 failed
    78 339 343 1 42 failed
    78 1300° F./4 h/AC 347 362 1 17 passed
    78 352 357 1 17 passed
    78 358 362 1 30 passed
    78 1325° F./4 h/AC 314 317 2 53 passed
    78 319 320 2 48 passed
    78 317 319 2 53 passed
    78 1350° F./4 h/AC 210 214 10 48 passed
    78 182 214 12 48 passed
    78 180 213 9 53 passed
  • [0017]
    Some of the aged wire samples representing cold reductions of 67-78% and aging treatments of 1250° F./4 hours and 1300° F./4 hours, respectively, were heated at 500° F. to simulate oil well conditions. Table IV shows the room-temperature tensile and wrap test results for the aged wire samples with and without the exposures at 500° F. for 24 hours and for 30 days at 500° F. The results presented in Table IV indicate that the simulated well-aged exposures at 500° F. had no detrimental effect on the tensile or wrap properties and, in some cases, the percent reduction in area (% R.A.) values were higher in the well-aged condition. The 500° F. exposures had no adverse effect on the tensile strength (U.T.S.) of aged wire material. An increase of up to about 30 ksi in the U.T.S. was observed for some of the cold-drawn-only wire after the 500° F. exposure.
  • [0000]
    TABLE IV
    Wire % Cold Aging 0.2% Wrap
    Diameter Drawn Treatment Exposure Y.S. U.T.S. % El. % R.A. Test
    0.034 in. 64 1250° F./4 h/AC 331 335 2 26 passed
    64 1250° F./4 h/AC 324 328 1 21 passed
    64 1250° F./4 h/AC 324 331 1 26 passed
    64 1250° F./4 h/AC 500° F./30 days 332 334 1 41 passed
    64 1250° F./4 h/AC 500° F./30 days 328 334 1 36 passed
    64 1250° F./4 h/AC 500° F./30 days 323 328 1 31 passed
    0.032 in. 67 1250° F./4 h/AC 355 358 1 46 passed
    67 1250° F./4 h/AC 331 344 1 54
    67 1250° F./4 h/AC 312 321 1 46
    67 1250° F./4 h/AC 500° F./30 days 342 352 1 54 passed
    67 1250° F./4 h/AC 500° F./30 days 335 344 1 54 passed
    67 1250° F./4 h/AC 500° F./30 days 347 350 1 54 passed
    0.0316 in. 69 None 278 303 1 47 pass
    69 None 500° F./24 h 293 327 1 32 pass
    69 None 500° F./24 h 297 333 2 37 pass
    69 None 500° F./24 h 302 329 2 37 pass
    69 1250° F./4 h/AC 356 361 1 27 pass
    69 1250° F./4 h/AC 362 364 1 27 fail
    69 1250° F./4 h/AC 350 356 1 22 pass
    69 1250° F./4 h/AC 500° F./24 h 350 354 1 43 pass
    69 1250° F./4 h/AC 500° F./24 h 349 352 1 33 pass
    69 1250° F./4 h/AC 500° F./24 h 352 356 1 43 pass*
    69 1300° F./4 h/AC 325 337 1 32 pass
    69 1300° F./4 h/AC 321 334 1 27 pass
    69 1300° F./4 h/AC 343 347 1 33 pass
    69 1300° F./4 h/AC 500° F./24 h 342 347 1 28 pass
    69 1300° F./4 h/AC 500° F./24 h 343 346 1 27 pass
    69 1300° F./4 h/AC 500° F./24 h 332 337 1 32 pass
    0.0293 in. 73 None 263 306 1 44 pass
    73 None 500° F./24 h 322 334 1 48 pass
    73 None 500° F./24 h 314 335 2 43 pass
    73 None 500° F./24 h 300 316 2 48 pass
    73 1250° F./4 h/AC 366 370 1 38 fail
    73 1250° F./4 h/AC 362 365 1 38 pass
    73 1250° F./4 h/AC 358 366 1 38 pass
    73 1250° F./4 h/AC 500° F./24 h 325 350 1 27 pass
    73 1250° F./4 h/AC 500° F./24 h 347 354 1 27 pass
    73 1250° F./4 h/AC 500° F./24 h 343 352 1 27 pass
    73 1300° F./4 h/AC 352 357 2 43 pass
    73 1300° F./4 h/AC 342 353 1 38 pass
    73 1300° F./4 h/AC 353 356 1 43 pass
    73 1300° F./4 h/AC 500° F./24 h 333 344 1 33 pass
    73 1300° F./4 h/AC 500° F./24 h 344 349 1 27 pass
    73 1300° F./4 h/AC 500° F./24 h 337 346 1 33 Pass
    0.0263 in. 78 None 286 320 1 53 Pass
    78 None 500° F./24 h 331 344 2 42 Fail
    78 None 500° F./24 h 318 328 2 30 fail
    78 None 500° F./24 h 328 335 2 36 fail
    78 1250° F./4 h/AC 350 358 1 53 fail
    78 1250° F./4 h/AC 328 346 1 42 fail
    78 1250° F./4 h/AC 350 355 1 53 fail
    78 1250° F./4 h/AC 500° F./24 h 333 350 1 48 fail
    78 1250° F./4 h/AC 500° F./24 h 347 354 1 53 pass
    78 1250° F./4 h/AC 500° F./24 h 332 337 1 42 fail
    78 1300° F./4 h/AC 347 362 1 17 pass
    78 1300° F./4 h/AC 352 357 1 17 pass
    78 1300° F./4 h/AC 358 362 1 30 pass
    78 1300° F./4 h/AC 500° F./24 h 357 362 1 42 pass
    78 1300° F./4 h/AC 500° F./24 h 337 354 1 36 pass
    78 1300° F./4 h/AC 500° F./24 h 347 349 1 36 pass
  • [0018]
    The effects of the various combinations of cold reduction and aging temperature on both tensile strength and wrap test ductility are illustrated in the drawing FIGURE. Lower amounts of cold reduction in combination with lower aging temperatures resulted in high U.T.S. levels of 330-360 ksi, but with a greater number of wrap test failures. Aging temperatures higher than 1300° F. resulted in lower tensile strength. However, aging the wire at 1300° F. for 4 hours resulted in consistently good wrap test performance at U.T.S. levels up to about 360 ksi. The best combinations of properties were obtained with cold reductions of about 67-78%.
  • Example 2
  • [0019]
    In a second set of tests, wire from another production heat of the UNS R00035 alloy was processed into fine wire. The heat chemistry of the additional wire material (Example 2) is presented in Table I above. The wire was cold drawn 68% R.C.S.A. to 0.031″ in diameter. The cold drawn wire was aged at various combinations of temperature and time as shown in Table V. Also, set forth in Table V are the results of room temperature tensile and wrap tests including the 0.2% offset yield strength (0.2% Y.S.) and the ultimate tensile strength (U.T.S.) in ksi, the percent elongation (% El.), the percent reduction in area (% R.A.), together with an indication whether the wire passed or failed the wrap test (Wrap Test). The aging heat treatment given to each test sample is shown in the column labeled “Age Treatment”. Some of the wire samples were given underaging heat treatments at 600° F. and 750° F., respectively, for 4 hours. The underaged samples were evaluated to determine if the desired properties could be achieved. The results for the underaged samples are also shown in Table V. The data presented in Table V confirm that the combination of at least about 325 ksi U.T.S. with acceptable wrap test ductility is obtained for the 68% cold-drawn samples aged at 1250-1325° F., although the most consistent results are obtained when the wire is aged at 1300° F. While two of the underaged samples provided acceptable results, most of the underaged samples did not achieve the desired combination of properties.
  • [0000]
    TABLE V
    Wire % Cold Aging Wrap
    Diameter Drawn Treatment 0.2% Y.S. U.T.S. % El. % R.A. Test
    0.0312 in. 68%  600° F./4 h/AC 318 324 1 14 failed
    313 332 1 19 passed
    309 327 2 14 passed
     750° F./4 h/AC 342 347 1 14 failed
    286 298 1 13 failed
    276 284 1 14 failed
    1250° F./1 h/AC 332 346 1 30 failed
    336 339 1 35 passed
    323 335 1 46 failed
    1250° F./4 h/AC 337 339 1 25 failed
    324 328 1 25 passed
    341 345 1 25 failed
    1275° F./1 h/AC 335 349 2 25 failed
    315 341 1 19 passed
    340 347 1 19 passed
    1275° F./4 h/AC 334 339 1 40 passed
    328 340 1 25 passed
    320 344 1 36 passed
    1300° F./1 h/AC 329 342 1 41 passed
    330 335 1 30 passed
    329 340 1 30 passed
    1300° F./4 h/AC 336 337 1 33 passed
    336 338 1 25 passed
    321 333 1 41 passed
    1325° F./1 h/AC 339 340 1 25 passed
    288 324 1 19 passed
    324 331 1 19 passed
    1325° F./4 h/AC 301 304 1 25 passed
    305 306 2 25 passed
    303 308 1 31 passed
  • [0020]
    The effects of heating rate and aging time were evaluated using additional samples of the 68% cold-drawn wire. Table VI shows the results of room temperature tensile and wrap tests including the 0.2% offset yield strength (0.2% Y.S.) and the ultimate tensile tensile strength (U.T.S.) in ksi, the percent elongation (% El.), the percent reduction in area (% R.A.), together with an indication whether the wire passed or failed the wrap test (Wrap Test). The aging heat treatment given to each test sample is shown in the column labeled “Age Treatment”. The data presented in Table VI show that the best combination of properties is obtained by aging at about 1300° F. for 4 hours.
  • [0000]
    TABLE VI
    Wire % Cold 0.2%
    Diameter Drawn Aging Treatment Y.S. U.T.S. % El. % R.A. Wrap Test
    Effects of Slow Heating
    0.0312 in. 68% slow heat 900-1250° F. (2 h), 336 340 1 30 Passed
    1250-1300° F. (3.5 h)/AC
    slow heat 900-1250° F. (2 h), 347 351 1 30 Passed
    1250-1300° F. (3.5 h)/AC
    slow heat 900-1250° F. (2 h), 350 352 1 25 Failed
    1250-1300° F. (3.5 h)/AC
    slow heat 900-1225° F. (4 h), 331 341 2 19 Passed
    1225-1275° F. (7 h)/AC
    slow heat 900-1225° F. (4 h), 314 338 2 14 Passed
    1225-1275° F. (7 h)/AC
    slow heat 900-1225° F. (4 h), 330 336 1 19 Passed
    1225-1275° F. (7 h)/AC
    slow heat 900-1250° F. (4 h), 336 338 1 36 Passed
    1250-1300° F. (7 h)/AC
    slow heat 900-1250° F. (4 h), 336 341 1 30 Passed
    1250-1300° F. (7 h)/AC
    slow heat 900-1250° F. (4 h), 337 342 1 30 Passed
    1250-1300° F. (7 h)/AC
    slow heat 900-1250° F. (4 h), 337 339 1 25 Passed
    1250-1300° F. (7 h)/4 h/AC
    slow heat 900-1250° F. (4 h), 315 337 1 25 Passed
    1250-1300° F. (7 h)/4 h/AC
    slow heat 900-1250° F. (4 h), 331 337 1 26 Passed
    1250-1300° F. (7 h)/4 h/AC
    slow heat 900-1250° F. (6 h), 330 331 1 30 Passed
    1250-1300° F. (10 h)/AC
    slow heat 900-1250° F. (6 h), 328 329 1 25 Passed
    1250-1300° F. (10 h)/AC
    slow heat 900-1250° F. (6 h), 333 335 1 26 Passed
    1250-1300° F. (10 h)/AC
    Effects of Aging Time
    0.0312 in. 1300° F./5 minutes/AC 323 343 1 19 Failed
    354 356 1 13 Passed
    319 341 1 19 Passed
    1300° F./15 minutes/AC 276 338 1 19 Failed
    335 355 1 13 Failed
    307 343 1 19 Passed
    1300° F./30 minutes/AC 349 349 1 25 Failed
    329 347 2 19 Passed
    317 344 1 25 Passed
    1300° F./1 h/AC 329 342 1 41 Passed
    330 335 1 30 Passed
    329 340 1 30 Passed
    1300° F./2 h/AC 324 342 1 30 Passed
    334 340 3 19 passed
    348 348 2 13 failed
    1300° F./4 h/AC 336 337 1 33 passed
    336 338 1 25 passed
    321 333 1 41 passed
    1300° F./8 h/AC 315 330 2 25 passed
    299 333 1 19 passed
    289 329 3 25 passed
    1300° F./1 h + 315 345 1 30 passed
    500° F./24 h
    1300° F./1 h + 317 331 1 36 passed
    500° F./24 h
    1300° F./1 h + 342 348 1 25 passed
    500° F./24 h
    1300° F./4 h + 341 345 1 30 passed
    500° F./24 h
    1300° F./4 h + 323 340 1 25 passed
    500° F./24 h
    1300° F./4 h + 328 344 1 25 passed
    500° F./24 h
    1300° F./1 h/slow cool + 299 354 1 19 failed
    500° F./24 h
    1300° F./1 h/slow cool + 340 350 1 25 passed
    500° F./24 h
    1300° F./1 h/slow cool + 312 355 1 25 passed
    500° F./24 h
  • [0021]
    Vacuum aging trials of small coils of the 68% cold drawn wire from Example 2 were performed. Small quantities of wire were coiled onto standard production spools so that the mass was comparable to that of a typical production order. For the first trial, the furnace setpoints were reduced to 1275° F. for 2 hours to avoid overheating the wire. The first trial resulted in lower % R.A. and some susceptibility to breakage during handling for subsequent corrosion testing. The wire breakage is believed to be attributable to more severe bending of the wire for the corrosion testing in combination with surface damage from the tool used to bend the wire specimens. A second trial was conducted using the preferred set point of 1300° F. for 4 hours. Table VII shows tensile and wrap test results for the two vacuum aged trials. Although the ductility of the wire as indicated by the % Elong. and the % R.A. increased relative to the first trial, none of the 1300° F. aged test samples passed the wrap test. Since the results for the bend test for the second trial were unexpected, the wire samples were analyzed to determine the reason for the failures. The failure analysis revealed that the wrap test breaks occurred because of defects on the surfaces of the wire samples.
  • [0022]
    A third trial was performed on six additional samples of wire that was aged the same way as in the first two trials. All six test samples passed the bend test in this trial. The test results are set forth at the bottom of Table VII.
  • [0000]
    TABLE VII
    Wire % Cold Aging 0.2% % % Wrap
    Diameter Drawn Treatment Y.S. U.T.S. El. R.A. Test
    First Trial
    0.0311 in. 68% 1275° F./2 h/ 344 348 1 19 passed
    Gas Quench
    1275° F./2 h/ 325 333 1 13 passed
    Gas Quench
    1275° F./2 h/ 333 354 1 13 passed
    Gas Quench
    Second Trial
    0.0311 in. 68% 1300° F./4 h/ 342 345 2 19 failed*
    Gas Quench
    1300° F./4 h/ 338 340 2 25 failed*
    Gas Quench
    1300° F./4 h/ 336 343 2 25 failed*
    Gas Quench
    Third Trial
    0.0312 in. 68% 1300° F./4 h/ 328 352 3 30 passed
    Gas Quench
    1300° F./4 h/ 329 343 3 25 passed
    Gas Quench
    1300° F./4 h/ 323 348 3 30 passed
    Gas Quench
    1300° F./4 h/ 323 353 3 30 passed
    Gas Quench
    1300° F./4 h/ 326 348 3 25 passed
    Gas Quench
    1300° F./4 h/ 327 350 3 25 passed
    Gas Quench
    *Failure analysis showed that fracture initiated at wire surface defects.
  • [0023]
    The terms and expressions which are employed herein are used as terms of description and not of limitation. There is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof. It is recognized that various modifications are possible within the invention described and claimed herein. Thus, the present invention may suitably comprise, consist essentially of, or consist of the steps of forming, annealing, drawing, and hardening as described herein. The invention illustratively disclosed herein suitably may be practiced in the absence of any step or parameter which is not specifically disclosed herein.

Claims (35)

  1. 1. A method of making wire comprising the steps of:
    forming a length of wire from an alloy comprising, in weight percent, about
    Carbon 0.03 max. Manganese 0.15 max. Silicon 0.15 max. Phosphorus 0.015 max. Sulfur 0.010 max. Chromium 19.00-21.00 Nickel 33.00-37.00 Molybdenum  9.00-10.50 Titanium 1.00 max. Boron 0.010 max. Iron 1.00 max.
    the balance being cobalt and the usual impurities;
    annealing said wire at a combination of temperature and time effective to provide a grain size of about ASTM 6 or finer;
    drawing the annealed wire such that the cross-sectional area of the wire is reduced by about 50 to 80%; and then
    hardening said alloy by heating the wire at a second combination of temperature and time effective to provide said alloy with a room temperature tensile strength of at least 300 ksi and sufficient ductility that when said wire is wrapped to provide a coil having an inside diameter substantially equal to the diameter of said wire and then unwrapped, said wire does not crack or break.
  2. 2. The method as claimed in claim 1 wherein the annealing step comprises the step of heating said wire at a temperature of about 1750 to 1850° F. for about 0.5 to 2 hours.
  3. 3. The method as claimed in claim 1 wherein the hardening step comprises heating the wire at a temperature of about 1250° F. to about 1325° F. for up to about 4 hours.
  4. 4. The method as claimed in claim 1 wherein the step of drawing the wire is performed such that the cross-sectional area of the wire is reduced by at least about 64%.
  5. 5. The method as claimed in claim 4 wherein the drawing step is performed such that the cross-sectional area of the wire is reduced by not more than about 78%.
  6. 6. The method as claimed in claim 5 wherein the drawing step is performed such that the cross-sectional area of the wire is reduced by not more than about 73%.
  7. 7. The method as claimed in claim 1 wherein the drawing step is performed such that the cross-sectional area of the wire is reduced by at least about 67%.
  8. 8. The method as claimed in claim 1 wherein the hardening step comprises heating the wire at not more than about 1300° F.
  9. 9. The method as claimed in claim 1 wherein:
    the drawing step is performed such that the cross-sectional area of the wire is reduced by about 64 to 78%; and
    the hardening step comprises heating the drawn wire at a temperature of about 1250-1300° F.
  10. 10. The method as claimed in claim 9 wherein the drawing step is performed such that the cross-sectional area of the wire is reduced by at least about 67%.
  11. 11. The method as claimed in claim 1 wherein:
    the drawing step is performed such that the cross-sectional area of the wire is reduced by about 64 to 73%; and
    the hardening step comprises heating the drawn wire at a temperature of about 1250-1325° F.
  12. 12. The method as claimed in claim 11 wherein the hardening step comprises heating the wire at a temperature not greater than about 1300° F.
  13. 13. The method as claimed in claim 12 wherein the drawing step is performed such that the cross-sectional area of the wire is reduced by not more then about 68%.
  14. 14. The method as claimed in claim 1 wherein:
    the drawing step is performed such that the cross-sectional area of the wire is reduced by about 67 to 78%; and
    the hardening step comprises heating the drawn wire at a temperature of about 1275-1300° F.
  15. 15. The method as claimed in claim 14 wherein the hardening step comprises heating the drawn wire at a temperature of about 1300° F.
  16. 16. The method as claimed in claim 1 wherein:
    the drawing step is performed such that the cross-sectional area of the wire is reduced by about 67 to 68%; and
    the hardening step comprises heating the drawn wire at a temperature of about 1275° F.
  17. 17. The method as claimed in claim 1 wherein:
    the drawing step is performed such that the cross-sectional area of the wire is reduced by about 67%; and
    the hardening step comprises heating the drawn wire at a temperature of about 1250° F.
  18. 18. A method of making flexible armored cable comprising the steps of:
    forming a length of wire from an alloy comprising, in weight percent, about
    Carbon 0.03 max. Manganese 0.15 max. Silicon 0.15 max. Phosphorus 0.015 max. Sulfur 0.010 max. Chromium 19.00-21.00 Nickel 33.00-37.00 Molybdenum  9.00-10.50 Titanium 1.00 max. Boron 0.010 max. Iron 1.00 max.
    the balance being cobalt and the usual impurities;
    annealing said wire at a combination of temperature and time effective to provide a grain size of about ASTM 6 or finer;
    drawing the annealed wire such that the cross-sectional area of the wire is reduced by about 50 to 80%; and then
    hardening said alloy by heating the wire at a second combination of temperature and time effective to provide said alloy with a room temperature tensile strength of at least 300 ksi and sufficient ductility that when said wire is wrapped to provide a coil having an inside diameter substantially equal to the diameter of said wire and then unwrapped, said wire does not crack or break; and then
    spirally winding the wire around an elongated core member to form a flexible encasement.
  19. 19. The method as claimed in claim 18 wherein the annealing step comprises the step of heating said wire at a temperature of about 1750 to 1850° F. for about 0.5 to 2 hours.
  20. 20. The method as claimed in claim 18 wherein the hardening step comprises heating the wire at a temperature of about 1250° F. to about 1325° F. for up to about 4 hours.
  21. 21. The method as claimed in claim 18 wherein the step of drawing the wire is performed such that the cross-sectional area of the wire is reduced by at least about 64%.
  22. 22. The method as claimed in claim 21 wherein the drawing step is performed such that the cross-sectional area of the wire is reduced by not more than about 78%.
  23. 23. The method as claimed in claim 22 wherein the drawing step is performed such that the cross-sectional area of the wire is reduced by not more than about 73%.
  24. 24. The method as claimed in claim 18 wherein the drawing step is performed such that the cross-sectional area of the wire is reduced by at least about 67%.
  25. 25. The method as claimed in claim 18 wherein the hardening step comprises heating the wire at not more than about 1300° F.
  26. 26. The method as claimed in claim 18 wherein:
    the drawing step is performed such that the cross-sectional area of the wire is reduced by about 64 to 78%; and
    the hardening step comprises heating the drawn wire at a temperature of about 1250-1300° F.
  27. 27. The method as claimed in claim 26 wherein the drawing step is performed such that the cross-sectional area of the wire is reduced by at least about 67%.
  28. 28. The method as claimed in claim 18 wherein:
    the drawing step is performed such that the cross-sectional area of the wire is reduced by about 64 to 73%; and
    the hardening step comprises heating the drawn wire at a temperature of about 1250-1325° F.
  29. 29. The method as claimed in claim 28 wherein the hardening step comprises heating the wire at a temperature not greater than about 1300° F.
  30. 30. The method as claimed in claim 29 wherein the drawing step is performed such that the cross-sectional area of the wire is reduced by not more then about 68%.
  31. 31. The method as claimed in claim 18 wherein:
    the drawing step is performed such that the cross-sectional area of the wire is reduced by about 67 to 78%; and
    the hardening step comprises heating the drawn wire at a temperature of about 1275-1300° F.
  32. 32. The method as claimed in claim 31 wherein the hardening step comprises heating the drawn wire at a temperature of about 1300° F.
  33. 33. The method as claimed in claim 18 wherein:
    the drawing step is performed such that the cross-sectional area of the wire is reduced by about 67 to 68%; and
    the hardening step comprises heating the drawn wire at a temperature of about 1275° F.
  34. 34. The method as claimed in claim 18 wherein:
    the drawing step is performed such that the cross-sectional area of the wire is reduced by about 67%; and
    the hardening step comprises heating the drawn wire at a temperature of about 1250° F.
  35. 35. A wire article comprising wire formed from a high strength, corrosion resistant alloy having the following composition in weight percent, about
    Carbon 0.03 max. Manganese 0.15 max. Silicon 0.15 max. Phosphorus 0.015 max. Sulfur 0.010 max. Chromium 19.00-21.00 Nickel 33.00-37.00 Molybdenum  9.00-10.50 Titanium 1.00 max. Boron 0.010 max. Iron 1.00 max.
    Wherein the balance of the alloy is cobalt and the usual impurities and the wire is characterized by a tensile strength in excess of 300 ksi and sufficient ductility that when the wire is wrapped to provide a coil having an inside diameter substantially equal to the diameter of the wire and then unwrapped, the wire does not crack or break.
US12721844 2009-03-12 2010-03-11 Ultra-High Strength, Corrosion Resistant Wire, a Method of Making Same, and a Method of Using Same Abandoned US20100230017A1 (en)

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