EP0765950B2 - Alliage à haute résistance et à coefficient d'expansion thermique faible - Google Patents

Alliage à haute résistance et à coefficient d'expansion thermique faible Download PDF

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Publication number
EP0765950B2
EP0765950B2 EP96306099A EP96306099A EP0765950B2 EP 0765950 B2 EP0765950 B2 EP 0765950B2 EP 96306099 A EP96306099 A EP 96306099A EP 96306099 A EP96306099 A EP 96306099A EP 0765950 B2 EP0765950 B2 EP 0765950B2
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Prior art keywords
alloy
total
alloys
niobium
thermal expansion
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EP96306099A
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German (de)
English (en)
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EP0765950B1 (fr
EP0765950A1 (fr
Inventor
John Scott Smith
Ladonna Sheree Hillis
Melissa Ann Moore
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Huntington Alloys Corp
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Inco Alloys International Inc
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Priority claimed from US08/696,487 external-priority patent/US5688471A/en
Application filed by Inco Alloys International Inc filed Critical Inco Alloys International Inc
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel

Definitions

  • This invention relates to low expansion alloys.
  • this invention relates to low expansion iron alloys containing about 40.5 to about 48 weight percent nickel.
  • the nickel-containing alloy tooling or fixtures used for curing graphite-epoxy composites must have very low thermal expansion coefficients.
  • the low coefficients of thermal expansion are necessary to decrease stresses arising from thermal expansion mismatch that occurs during heating of resin-containing tooling to curing temperatures.
  • the low-expansion alloy system of 36 to 42 weight percent nickel and balance of essentially iron has been commercially used for these tooling applications.
  • These iron-base alloys are, however, inherently soft, difficult to weld in large sections, lack dimensional stability after thermomechanical processing, and are difficult to machine. For example, the knives used to remove graphite epoxy composites from the tooling routinely cut into and mar the tooling's surface.
  • Another problem with these iron-base low expansion alloys is is general corrosion that accelerates during the curing of graphite epoxy tooling.
  • Structural graphite epoxy composites have CTEs that are highly variable with orientation. Typically graphite-epoxy composites have CTEs that range from 1.8 to 9.0 x10 -6 m/m/°C (1.0 to 5.0 x 10 -6 in/in/°F) depending upon orientation. The mean CTE of this composite is about 5.4 x 10 -6 m/m/°C (3.0 x 10 -6 in/in/°F). The alloys used for this tooling have a lower CTE than the composite being cured. The low CTE tooling provides a constant and uniform compressive force during heating of the composites from room to curing temperatures.
  • This compressive force reduces porosity, permits tight tolerances (e.g., ⁇ 0.0051 cm or ⁇ 0.002 in or less), and provides high quality composite surfaces.
  • CTE of the alloy must be 4.9 x 10 -6 m/m/°C (2.7 x 10 -6 in/in/°F) or less.
  • the alloy of the invention provides a low coefficient of thermal expansion alloy having a CTE of about 4.9 x10 -6 m/m/°C or less at 204°C and a relatively high strength is defined in the accompanying claims. Alloys of the invention may be aged to a Rockwell C hardness of at least about 30.
  • niobium and titanium may be used in combination to provide an age hardenable alloy while maintaining a relatively low CTE.
  • the alloys of the invention are readily aged to produce a hardness of at least 30 on the Rockwell “C” (RC) scale.
  • NILO® alloy 36 typically only has a hardness of 71 on the Rockwell “B” (RB) scale (NILO is a trademark of the Inco family of companies).
  • the alloys of the invention are uniquely characterized by a relatively low CTE in combination with excellent marring resistance.
  • Table 1 HEAT C MN FE S SI NI CR AL TI NG CO MO NB TA NB + TA 1 * 0.004 0.2 56.7 0.1101 0.1 38.17 ⁇ 0.1 0.33 1.5 ⁇ 0.1 ⁇ 0.1 ⁇ 0.1 2.9 0.001 2.9 2 * 0.005 0.2 54.9 0.001 0.1 40.09 ⁇ 0.1 0.12 1.5 ⁇ 0.1 ⁇ 0.1 ⁇ 0.1 2.9 0.001 2.9 3 * 0.018 0.2 54.8 0.001 0.1 40.24 ⁇ 0.1 0.30 1.5 ⁇ 0.1 ⁇ 0.1 ⁇ 0.1 2.9 0.001 2.9 4 * 0.003 0.2 54.8 0.001 0.1 40.07 ⁇ 0.1 0.32 1.5 ⁇ 0.1 ⁇ 0.1 ⁇ 0.1 2.9 0.001 2.9 5 * 0.005 0.2 54.4 0.001 0.1 40.06 ⁇ 0.1 0.51 1.5 ⁇ 0.1 ⁇ 0.1 ⁇ 0.1 2.9 0.001 2.9 6 * 0.004 0.2 52.7 0.001 0.1 41.93
  • Table 2 below provides coefficient of thermal expansion and hardness data for alloys that were warm worked and aged at 1200°F (649°C) for 8 hours then air cooled.
  • Table 2 provides coefficient of thermal expansion and hardness data for alloys that were warm worked and aged at 1200°F (649°C) for 8 hours then air cooled.
  • the CTE of graphite-epoxy composites at 360°F (182°C) is 3.1 x 10 -6 in/in/°F (5.6 x 10 -6 m/m/°C).
  • Figures 1 and 2 illustrate that CTE reaches a minimum above about 42.3% nickel.
  • alloys of the invention contain sufficient nickel to provide a relatively low CTE of less than or equal to about 4.9 x 10 -6 m/m/°C (2.7 x10 -6 in/in/°F) at 204°C (400°F).
  • the CTE is less than or equal to about (4.5 x 10 -6 m/m/°C (2.5 x 10 -6 in/in/°F) at 204°C (400°F).
  • CTE in / in / °F 245.29 ⁇ 10 - 6 - 11.26 ⁇ 10 - 6 Ni + 0.13 ⁇ 10 - 6 Ni 2 + 3.77 ⁇ 10 - 6 Al
  • Figure 3 illustrates that total niobium and tantalum must be limited to about 3.7 weight percent to maintain a CTE less than 4.9 x 10 -6 m/m/°C. At total niobium plus tantalum concentrations above about 3.5 weight percent, the 204°C (400°F) CTE of the alloy dramatically increases.
  • tantalum is maintained at concentrations below about 0.25 weight percent. Tantalum concentrations above about 0.25 weight percent are believed to be detrimental to weldability and phase segregation. Alloys containing less than 0.25 weight percent tantalum may be readily formed into large sections free of both macro- and micro-segregation. Furthermore, an optional addition of at least about 0.15 weight percent manganese facilitates hot working of the alloy. In addition, boron may optionally be added to the alloy in quantities up to about 0.01 weight percent.
  • Table 6 below provides hardness data for annealed and aged alloys of the invention.
  • the alloy of Table 6 were all annealed at 1700°F (927°C) prior to aging.
  • Tables 4-6 illustrate that the alloys of the invention may be readily age hardened to hardness levels at least as high as about 30 on the Rockwell C scale. Most advantageously, alloys are aged to a hardness of at least about 35 on the Rockwell C scale. Advantageously, the alloys are aged at a temperature between 1000 and 1400°F (538 and 760°C). Most advantageously, alloys are aged at a temperature between about 1100 and 1300°F (593 to 704°C) for optimum age hardening. It has been discovered that thermomechanical processing followed by an aging heat treatment further optimizes hardness of the alloy.
  • Table 7 compares oxidation resistance of alloys of the invention to alloy 36 Ni-Fe after exposure to air at 371°C for 560 hours.
  • alloy 36 oxidizes nearly twice as rapidly as alloys of the invention at typical curing temperature for graphite-epoxy composites. Although these alloys lack the oxidation resistance of chromium-containing alloys, the increased oxidation resistance of the invention significantly reduces tooling maintenance. For example, facing plates require less grinding, polishing or pickling to maintain a smooth metal surface.
  • Table 8 demonstrates the dimensional stability of alloys of the invention in comparison to 36 Ni-Fe alloys. TABLE 8 HEAT CREEP STRENGTH, MPa 11 >690 12 >690 D (Alloy 36) 55
  • Heat D was annealed prior to testing. Heats 11 and 12 were annealed and aged as above.
  • the age hardened alloys of the invention provide at least a ten-fold increase in creep resistance. This increase in creep resistance provides excellent dimensional stability that effectively resists deformation during curing. The alloys dimensional stability allows significant reductions of the size and amount of materials necessary to produce durable tooling.
  • the alloy of the invention is described by alloys having the composition of Table 9 below. TABLE 9 BROAD INTERMEDIATE NARROW NOMINAL Ni 42.3-48 42.3-46 42.3-45 43.5 Nb 2-3.7 2.5 - 3.6 3-3.5 3.3 Ti 0.75-2 0.9-1.9 1-1.8 1.4 Al 0-1 0.05-0.8 0.05-0.6 0.2 C 0-0.1 0-0.05 0.01 Mn 0-1 0-0.5 0.3 Si 0-1 0-0.5 - Cu 0-1 0.5 - Cr 0-1 0-0.5 - Co 0-5 0-2 - B 0-0.01 0-0.005 - W, V 0-2 0-1 - Ta 0-0.25 Mg, Ca, Ce (Total) 0-0.1 0-0.05 - Y, Rare Earths (Total) 0-0.5 0-0.1 - S 0-0.1 0-0.05 - P 0-0.1 0-0.05 - N 0-0.1 0-0.05 - Fe Balance + Incidental Impurities Balance + Incidental Impurities Balance + Incidental
  • the alloy of the invention provides alloys having a coefficient of thermal expansion of 2.7 x 10 -6 in/in/°F (5.5 x 10 -6 m/m/°C) or less with a minimum hardness of RC 30. With a hardness above RC 30, composite tooling alloys provide excellent resistance to scratching and marring. In addition, age hardening increases the yield strength of the alloy and machinability of the alloy. The alloy has tested to be excellent with the drop weight and bend tests. The alloy may be readily welded with NILO® filler metals 36 and 42. Finally, the alloys of the invention provide improved oxidation resistance and dimensional stability over conventional iron-nickel low coefficient of thermal expansion alloys.
  • the alloys of the invention provides an especially useful material for tooling that are used to fabricate graphite-epoxy composites or other low CTE composites under compression.
  • the alloys of the invention are expected to be useful for high strength electronic strips, age hardenable lead frames and mask alloys for tubes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Heat Treatment Of Steel (AREA)
  • Materials For Medical Uses (AREA)

Claims (11)

  1. Un alliage à haute résistance et à faible coefficient de dilatation thermique, CTE, de 4,9 x 10-6m/m/°C ou moins à 204°C, constitué, exprimé en pourcentage en poids, de 42, 3 à 48 % de nickel, 2 à 3,7 % de niobium, 0,75 à 2 % de titane, 3,7 ou moins pour le total du niobium plus le tantale, 0 à 1 % d'aluminium, 0 à 0,1 % de carbone, 0 à 1 de manganèse, 0 à 1 % de silicium, 0 à 1 % de cuivre, 0 à 1 % de chrome, 0 à 5 % de cobalt, 0 à 0,01 % de bore, 0 à 2 % de tungstène, 0 à 2 % de vanadium, 0 à 0,1 % du total du magnésium, calcium et cérium, 0 à 0,5 % du total de l'yttrium et de terres rares, de 0 à 0,1 % de soufre, 0 à 0,1 de phosphore, 0 à 0,1 % d'azote et le reste étant du fer et d'éventuelles impuretés.
  2. L'alliage selon la revendication 1, comprenant de 42,3 à 46 % en poids de nickel, 2,5 à 3,6 % de niobium, 0,9 à 1,9 de titane et 0,05 à 0,8 % d'aluminium.
  3. L'alliage selon la revendication 1 ayant une dureté d'au moins 30 sur l'échelle Rockwell C.
  4. Un alliage à haute résistance et à faible coefficient de dilatation thermique, CTE, de 4,9 x 10-6m/m/°C ou moins à 204°C, constitué, exprimé en pourcentage en poids, de 42,3 à 46 % de nickel, 2 à 3,6 % de niobium, 0,9 à 1,9 % titane, 0,05 à 0,8 % d'aluminium, 0 à 0,1 % de carbone, 0 à 1 % de manganèse, 0 à 1 % de silicium, 0 à 1 % de cuivre, 0 à 0,5 de chrome, 0 à 5 % de cobalt, 0 à 0,01 % de bore, 0 à 2 % de tungstène, 0 à 2 % de vanadium 0 à 0,05 % du total du magnésium, calcium et cérium, 0 à 0,5 % du total de l'yttrium et de terres rares, 0 à 0,1 % de soufre, 0 à 0,1 % de phosphore, 0 à 0,1 % d'azote, 3,6 % ou moins du total du niobium plus le tantale, et le reste étant du fer et d'éventuelles impuretés.
  5. L'alliage selon la revendication 4, comprenant de 42,3 à 45 % en poids de nickel.
  6. L'alliage selon la revendication 4, comprenant de 3 à 3,5 % en poids de niobium, 1 à 1,8 % en poids de titane et 0,05 à 0,6 % en poids d'aluminium.
  7. L'alliage selon la revendication 4, comprenant de 0 à 0,05 % en poids de carbone, 0 à 0,5 % de manganèse, 0 à 0,5 % de silicium, 0 à 0,5 % de cuivre, 0 à 0,5 % de chrome, 0 à 2 % de cobalt, 0 à 0,005 de bore, 0 à 1 % de tungstène, 0 à 1 % de vanadium, 0 à 0,05 % du total du magnésium, calcium et cérium, 0 à 0,01 % total de l'yttrium et des terres rares, 0 à 0,05 % de soufre, 0 à 0,05 % de phosphore, moins de 0,25 % en poids de tantale et de 0 à 0,05 % en poids d'azote.
  8. L'alliage selon la revendication 4, ayant une dureté d'au moins 30 sur l'échelle Rockwell C.
  9. Un alliage à haute résistance et à faible coefficient de dilatation thermique, CTE, de 4,9 x 10-6m/m/°C ou moins à 204°C, constitué, exprimé en pourcentage en poids, de 42,3 à 45 % de nickel, 3 à 3,5 % de niobium, 1 à 1,8 % de titane, 0 à 0,6 % d'aluminium, 0 à 0,05 % de carbone, 0 à 0,5 de manganèse, 0 à 0,5 % de silicium, 0 à 0,5 % de cuivre, 0 à 2 % de cobalt, 0 à 0,005 % de bore, 0 à 1 % de tungstène, 0 à 1 de vanadium, 0 à 0,1 % du total de l'yttrium et de terres rares, 0 à 0,05 % de soufre, 0 à 0,05 % de phosphore, 0 à 0,05 % d'azote, 3,5 % ou moins du total du niobium plus le tantale, 0 à 0,25 % de tantale et le reste étant du fer et d'éventuelles impuretés.
  10. L'alliage selon la revendication 9 ayant une dureté d'au moins 30 sur l'échelle Rockwell C.
  11. Utilisation d'un alliage, telle que définie sur l'une quelconque des revendications 1 à 10 pour la fabrication d'outillage destiné à la fabrication, à faible coefficient de dilatation thermique CTE, de composites, graphite-epoxy, ou pour la fabrication de bandes électroniques, de châssis conducteurs durcissables par le vieillissement, ou bien d'alliages de masques pour des tubes.
EP96306099A 1995-08-25 1996-08-21 Alliage à haute résistance et à coefficient d'expansion thermique faible Expired - Lifetime EP0765950B2 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US51967895A 1995-08-25 1995-08-25
US519678 1995-08-25
US08/696,487 US5688471A (en) 1995-08-25 1996-08-14 High strength low thermal expansion alloy
US696487 1996-08-14

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EP0765950A1 EP0765950A1 (fr) 1997-04-02
EP0765950B1 EP0765950B1 (fr) 2001-10-17
EP0765950B2 true EP0765950B2 (fr) 2010-01-20

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JP (1) JPH09165653A (fr)
DE (1) DE69615977T3 (fr)
ES (1) ES2161983T3 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10435780B2 (en) 2009-06-11 2019-10-08 Genius Solutions Engineering Company Low CTE slush molds with textured surface, and method of making and using the same
JP6244979B2 (ja) * 2014-02-27 2017-12-13 新日鐵住金株式会社 低熱膨張合金

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0482889A2 (fr) † 1990-10-26 1992-04-29 Inco Alloys International, Inc. Métal d'apport de sondage pour alliages à bas coefficient de dilatation thermique
JPH04180542A (ja) † 1990-11-14 1992-06-26 Hitachi Metals Ltd 低熱膨張高強度材料
JPH04202642A (ja) † 1990-11-30 1992-07-23 Nkk Corp メッキ性，ハンダ性，繰返し曲げ特性に優れた高強度低熱膨脹Ｆｅ―Ｎｉ合金およびその製造方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3093518A (en) * 1959-09-11 1963-06-11 Int Nickel Co Nickel alloy
US3514284A (en) * 1966-06-08 1970-05-26 Int Nickel Co Age hardenable nickel-iron alloy for cryogenic service
US3705827A (en) * 1971-05-12 1972-12-12 Carpenter Technology Corp Nickel-iron base alloys and heat treatment therefor
US4445943A (en) * 1981-09-17 1984-05-01 Huntington Alloys, Inc. Heat treatments of low expansion alloys
JP2669789B2 (ja) * 1994-08-11 1997-10-29 株式会社東芝 管内部品

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0482889A2 (fr) † 1990-10-26 1992-04-29 Inco Alloys International, Inc. Métal d'apport de sondage pour alliages à bas coefficient de dilatation thermique
JPH04180542A (ja) † 1990-11-14 1992-06-26 Hitachi Metals Ltd 低熱膨張高強度材料
JPH04202642A (ja) † 1990-11-30 1992-07-23 Nkk Corp メッキ性，ハンダ性，繰返し曲げ特性に優れた高強度低熱膨脹Ｆｅ―Ｎｉ合金およびその製造方法

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Publication number Publication date
EP0765950B1 (fr) 2001-10-17
ES2161983T3 (es) 2001-12-16
EP0765950A1 (fr) 1997-04-02
DE69615977T2 (de) 2002-04-04
JPH09165653A (ja) 1997-06-24
DE69615977D1 (de) 2001-11-22
DE69615977T3 (de) 2010-05-06

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