EP0175130B1 - Verfahren zur Verleihung von Festigkeit an intermetallischen Phasen - Google Patents

Verfahren zur Verleihung von Festigkeit an intermetallischen Phasen Download PDF

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EP0175130B1
EP0175130B1 EP85110021A EP85110021A EP0175130B1 EP 0175130 B1 EP0175130 B1 EP 0175130B1 EP 85110021 A EP85110021 A EP 85110021A EP 85110021 A EP85110021 A EP 85110021A EP 0175130 B1 EP0175130 B1 EP 0175130B1
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Prior art keywords
boron
alloy
aluminum
composition
ductility
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English (en)
French (fr)
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EP0175130A1 (de
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Shyh-Chin Huang
Keh-Minn Chang
Alan Irwin Taub
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General Electric Co
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General Electric Co
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/04—Amorphous alloys with nickel or cobalt as the major constituent

Definitions

  • the intermediate phases and intermetallic compounds often exhibit properties entirely different from those of the component metals comprising the system. They also frequently have complex crystallographic structures.
  • the lower order of crystal symmetry and fewer planes of denes atomic population of these complex crystallographic structures may be associated with certain differences in properties, e.g. greater hardness, lower ductility, lower electrical conductivity of the intermediate phases as compared to the properties of the primary solid solutions.
  • Another object is to provide an alloy of nickel and aluminum capable of operating at elevated temperatures for sustained periods of time.
  • Another object is to provide a nickel aluminum alloy having an L1 2 type crystal structure but having significant ductility and strength.
  • Another object is to provide an alloy of aluminum and nickel in which another element is substituted for a portion of the aluminum and which has a unique combination of physical properties.
  • objects of the invention can be achieved by providing a rapidly solidified alloy composition having an L1 2 crystal structure and having a composition as follows: where 98 ⁇ y ⁇ 99.9 and X is a substituent metal selected from the group consisting of vanadium and silicon.
  • substituent metal a metal which takes the place of and in this way is substituted for another and different metal, where the other metal is part of a combination of metals forming an essential constituent of an alloy system.
  • Ni 3 AI the constituent metals are nickel and aluminum.
  • the metals are present in the stoichiometric atomic ratio of 3 nickel atoms for each aluminum atom in this system. It had been discovered that a desirable crystal form and accompanying superior physical properties can be achieved by forming a single crystal of Ni 3 AI.
  • polycrystalline Ni 3 AI is quite brittle and shatters under stress such as is applied in efforts to form the material into useful objects or to use such an article.
  • substituent metals can be beneficially substituted in part for the constituent aluminum and hence these substituted metals are designated and known herein as substituent metals i.e. as an aluminum substituent in the Ni 3 AI structure.
  • substituent metals i.e. as an aluminum substituent in the Ni 3 AI structure.
  • valuable and beneficial properties are imparted to the rapidly solidified compositions which have the stoichiometric proportions but which have a substituent metal as a quaternary ingredient of such rapidly solidified alloy systems.
  • the alloy compositions of the present invention must contain a first or primary ingredient or component and a second ingredient or component different from the first.
  • the compositions must also contain boron as a tertiary ingredient as taught herein and as taught in copending application EP-A-0110268 referred to above, and must further contain a quaternary component or ingredient as a substituent for aluminum as taught in the subject specification.
  • the first constituent or ingredient is preferably nickel.
  • first constituent and the second constituent must be present in substantially stoichiometric atomic ratios.
  • An example is the nickel aluminide in which three atoms are present as the primary component constituent for each aluminum constituent which is present.
  • the composition which is formed must have a preselected intermetallic phase having a crystal structure of the L1 2 type and must have been formed by cooling the melt at a cooling rate of at least about 10 3o C per second to form a solid body the principal phase of which is the L1 2 type crystal structure in either its ordered or disordered state.
  • the melt composition from which the structure is formed must have the first constituent and second constituent present in the melt in an atomic ratio of approximately 3:1.
  • compositions having this combination of ingredients and which are subjected to the rapid solidification technique have surprisingly high values for both the strain to fracture after yield and for the 0.2% offset yield stress.
  • the values of the strain to fracture generally declines so that a preferred range for the boron tertiary additive is between 0.5 and 1.5%.
  • the quaternary ingredient which may be beneficially included in a composition for rapid solidification as a substituent to make unprecedented improvements in the properties include the elements vanadium and silicon.
  • an intermetallic phase having an L1 2 type crystal structure is first selected.
  • the selection criteria will depend upon the end use environment which, in turn, determines the attributes, such as strength, ductility, hardness, corrosion resistance and fatigue strength, required of the material selected.
  • Ni 3 AI nickel aluminide
  • Ni 3 AI nickel aluminide
  • Nickel aluminide has high hardness and is stable and resistant to oxidation and corrosion at elevated temperatures which makes it attractive as a potential structural material.
  • single crystals of Ni 3 AI exhibit good ductility in certain crystallographic orientations, the polycrystalline form, i.e., the form of primary significance from an engineering standpoint, has low ductility and falls in a brittle manner intergranularly.
  • FeC face centered cubic
  • the selected intermetallic phase is provided as a melt whose composition corresponds to that of the preselected intermetallic phase.
  • the melt composition will consist essentially of the atoms of the two components of the intermetallic phase in an atomic ratio of approximately 3:1 and is modified with boron in an amount of from about 0.01 to 2.5 at.%.
  • the components will be two different elements, but, while still maintaining the approximate atomic ratio of 3: 1, one or more elements may, in some cases, be partially substituted for one or both of the two elements which form the intermetallic phase.
  • the melt should ideally consist only of the atoms of the intermetallic phase and atoms of boron, it is recognized that occasionally and inevitably other atoms of one or more incidental impurity atoms may be present in the melt.
  • the melt is next rapidly cooled at a rate of at least about 10 3 °C/sec to form a solid body, the principal phase of which is of the L1 2 type crystal structure in either its ordered or disordered state.
  • the rapidly solidified solid body will principally have the same crystal structure as the preselected intermetallic phase, i.e., the L1 2 type, the presence of other phases, e.g., borides, is possible. Since the cooling rates are high, it is also possible that the crystal structure of the rapidly solidified solid will be disordered, i.e., the atoms will be located at random sites on the crystal lattice instead of at specific periodic positions on the crystal lattice as is the case with ordered solid solutions.
  • splat cooling There are several methods by which the requisite large cooling rates may be obtianed, e.g., splat cooling.
  • a preferred laboratory method for obtaining the requisite cooling rates is the chill-block melt spinning process.
  • molten metal is delivered from a crucible through a nozzle, usually under the pressure of an inert gas, to form a free-standing stream of liquid metal or a column of liquid metal in contact wiht the nozzle.
  • the stream of liquid metal is then impinged onto or otherwise placed in contact with a rapidly moving surface of a chill-block, i.e., a cooling substrate, made of a material such as copper.
  • the material to be melted can be delivered to the crucible as separate solids of the elements required and melted therein by means such as an induction coil placed around the crucible or a "master alloy" can first be made, comminuted, and the comminuted particles placed in the crucible.
  • a "master alloy” can first be made, comminuted, and the comminuted particles placed in the crucible.
  • the liquid melt contacts the cold chill-block, it cools rapidly, from about 10 3 °C/sec to 10 7 °C/sec, and solidifies in the form of a continuous length of a thin ribbon whose width is considerably larger than its thickness.
  • a more detailed teaching of the chill-block melt spinning process may be found, for example, in U.S. Patents 2,825,108, 4,221,2517, and 4,282,921 which are herein incorporated by reference.
  • a heat of a composition corresponding to about 3 atomic parts nickel to 1 atomic part aluminum and 1 atomic percent boron was prepared, comminuted, and about 60 grams of the pieces were delivered into an alumina crucible of a chill-block melt spinning apparatus.
  • the composition had the formula:
  • the crucible terminated in a flat-bottomed exit section having a slot 0.25 (6.35 mm) inches by 25 mils (0.635 mm) therethrough.
  • a chill block in the form of a wheel having faces 10 inches (25.4 cm) in diameter wnn a (nm) thickness of 1.5 incnes (3.8 cm), maae of H-12 tool steel, was oriented vertically so that the rim surface could be used as the casting (chill) surface when the wheel was rotated about a horizontal axis passing through the centers of and perpendicular to the wheel faces.
  • the crucible was placed in a vertically up orientation and brought to within about 1.2 to 1.6 mils (30-40 ⁇ m) of the casting surface with the 0.25 inch (6.35 mm) length dimension of the slot oriented perpendicular to the direction of rotation of the wheel.
  • the wheel was rotated at 1200 rpm.
  • the melt was heated to between about 1350 and 1450°C.
  • the melt was ejected as a rectangular stream onto the rotating chill surface under the pressure of argon at about 1.5 psi to produce a long ribbon which measured from about 40-70 pm in thickness by about 0.25 inches (6.35 mm) in width.
  • the ribbons were tested for bend ductility and a value of 1.0 was found. This value of bend ductility designates that the ribbon can be bent fully to 180°C without fracture.
  • Example 1 The procedure of Example 1 was repeated using the same equipment to prepare a master heat of the boron doped nominal Ni 3 AI composition but one which was modified to the following composition:
  • the ribbons were tested for bend ductility and a value of 0.04 was found for the ribbon thus prepared. This value of band ductility was calculated by dividing the ribbon thickness by the bend radius at which the ribbon fractures.
  • the stress in ksi for the unmodified aluminide is shown by the lower plot and this composition has a stress of 135 ksi at yield.
  • the stress at yield for the uppermost plot is some 37% higher at 185 ksi and this is a significant and unexpected advance in the ability of those skilled in this art to increase the tensile properties of the rapidly solidified, boron doped nickel aluminide base alloys.
  • Example 6 which involved the incorporation of the vanadium in the rapidly solidified boron doped tri-nickel aluminide as a substituent for aluminum also resulted in a composition having a bend ductility test value of 1.0. Further this composition was found to be equiaxed.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Continuous Casting (AREA)

Claims (6)

1. Schnell verfestigende Bor-dotierte Legierung auf Nickel-Aluminid-Basis mit einer Kristallstruktur vom LI2-Typ, welche Legierung eine Zusammensetzung mit der Formel
Figure imgb0007
worin 98≤y≤99,9 ist und worin X ausgewählt ist aus der Gruppe bestehend aus Vanadium und Silicium.
2. Aluminid nach Anspruch 1, in welchem X Vanadium ist.
3. Aluminid nach Anspruch 1, in welchem X Silicium ist.
4. Schnell verfestigende Bor-dotierte Legierung auf Nickel-Aluminid-Basis mit einer Kristallstruktur vom L12-Typ, wobei die Legierung eine Zusammensetzung mit der Formel
Figure imgb0008
ist, worin X ausgewählt ist aus der Gruppe bestehend aus Vanadium und Silicium.
5. Aluminid nach Anspruch 4, worin X Silicium ist.
6. Aluminid nach Anspruch 4, worin X Vanadium ist.
EP85110021A 1984-09-04 1985-08-08 Verfahren zur Verleihung von Festigkeit an intermetallischen Phasen Expired EP0175130B1 (de)

Applications Claiming Priority (2)

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US64732784A 1984-09-04 1984-09-04
US647327 1996-05-06

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EP0175130A1 EP0175130A1 (de) 1986-03-26
EP0175130B1 true EP0175130B1 (de) 1988-04-27

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JP (1) JPS6176640A (de)
DE (1) DE3562388D1 (de)
IL (1) IL75694A (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104018015A (zh) * 2014-06-13 2014-09-03 四川法拉特不锈钢铸造有限公司 一种镍合金液的熔炼除气方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4613368A (en) * 1985-10-03 1986-09-23 General Electric Company Tri-nickel aluminide compositions alloyed to overcome hot-short phenomena
CH669396A5 (de) * 1986-09-02 1989-03-15 Bbc Brown Boveri & Cie

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GB1448862A (en) * 1973-01-12 1976-09-08 Nat Res Dev Intermetallic compound materials
US4478791A (en) * 1982-11-29 1984-10-23 General Electric Company Method for imparting strength and ductility to intermetallic phases

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104018015A (zh) * 2014-06-13 2014-09-03 四川法拉特不锈钢铸造有限公司 一种镍合金液的熔炼除气方法
CN104018015B (zh) * 2014-06-13 2016-03-30 四川法拉特不锈钢铸造有限公司 一种镍合金液的熔炼除气方法

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DE3562388D1 (en) 1988-06-01
EP0175130A1 (de) 1986-03-26
IL75694A0 (en) 1985-11-29
IL75694A (en) 1988-09-30

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