EP0302803A2 - Verfahren zur Herstellung hochschmelzender Legierungen - Google Patents

Verfahren zur Herstellung hochschmelzender Legierungen Download PDF

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Publication number
EP0302803A2
EP0302803A2 EP88420277A EP88420277A EP0302803A2 EP 0302803 A2 EP0302803 A2 EP 0302803A2 EP 88420277 A EP88420277 A EP 88420277A EP 88420277 A EP88420277 A EP 88420277A EP 0302803 A2 EP0302803 A2 EP 0302803A2
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EP
European Patent Office
Prior art keywords
alloy
alloys
initial
base element
melting point
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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.)
Withdrawn
Application number
EP88420277A
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English (en)
French (fr)
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EP0302803A3 (de
Inventor
John Raymond Mihalisin
Michelle Kriley Tripucka
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Howmet Corp
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Howmet Corp
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Filing date
Publication date
Application filed by Howmet Corp filed Critical Howmet Corp
Publication of EP0302803A2 publication Critical patent/EP0302803A2/de
Publication of EP0302803A3 publication Critical patent/EP0302803A3/de
Withdrawn legal-status Critical Current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
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/023—Alloys based on nickel

Definitions

  • the present invention relates to a method of making high melting point alloys through melting.
  • the conventional process for formulating high melting point alloys from constituent materials through melting involves two stages.
  • the non-reactive elements comprising a portion of the high melting point alloy are refined to remove as much oxygen and nitrogen as possible, usually through the addition of carbon to promote a carbon boil.
  • the elements which readily react with oxygen and nitrogen and comprise the reactive portion of the high melting point alloy are added to the non-reactive charge.
  • the reactive elements are added late in the vacuum induction melt cycle so that the time these elements spend in the vacuum furnace is minimized to limit any reaction with the crucible lining and residual air in the furnace.
  • the reactive elements must remain in the melt for a time sufficient to achieve homogenization.
  • the reactive elements are added, for the most part, as elemental additions rather than mixtures or compounds of several reactive elements. Because allowances must be made to compensate for the wide variety in melting points and densities among the elemental additions, the conventional process for pro­ducing high melting point alloys is both time consuming and dif­ficult to automate.
  • the conventional process suffers from the further disadvan­tage that exothermic reactions occur when particular reactive elements are added to the melt.
  • exothermic reactions occur when particular reactive elements are added to the melt.
  • an exothermic reac­tion occurs when aluminum is added to a melt containing nickel.
  • Such exothermic reactions cause high temperature excursions which accelerate the reaction of the melt with the refractory lining of the crucible, resulting in both shortened crucible life and also increased contamination in the high melting point alloy.
  • the high melting point alloy is comprised of a combination of a base element selected from the iron group of the Periodic Table and a plurality of metallic elements other than the base element.
  • At least one first initial alloy is pro­vided.
  • the first initial alloy consists essentially of the base element and at least one of the metallic elements.
  • the metallic elements other than the base element in the first initial alloys are relatively non-reactive in the molten state.
  • At least one second initial alloy is provided.
  • the second initial alloy con­sists essentially of the base element and at least one of the me­tallic elements.
  • the metallic elements in the second initial alloys are relatively reactive in the molten state. Amounts of the first and second initial alloys are selected to yield a pre­determined composition of the high melting point alloy upon melting. The selected amounts of the first and second initial alloys are melted to form a molten mixture having the predeter­mined composition. The molten mixture is then solidified.
  • the method of making a high melting point alloy of the pres­ent invention involves separately pre-refining the reactive and non-reactive charge materials as initial alloys, generally as an alloy of a base element selected from the iron group of the Peri­odic Table, such as nickel, and at least one metallic element other than the base element. While the invention is disclosed using embodiments containing Ni as the base metal, Co, Fe, and Cr-based alloys are also operable.
  • desired high melting point alloy compositions amounts of the initial alloys are se­lected to yield the desired composition. These amounts are charged in a suitable means for melting, such as a vacuum in­duction furnace, and melted. Because the initial alloys have already been refined, no further refining steps are necessary. In addition, because the melting point and density disparities encountered with elemental additions are significantly less with the initial alloys, the charge comprised of such initial alloys can be melted rapidly and homogenization can be achieved in a relatively short period of time.
  • At least one first initial alloy consisting essentially of the base element and at least one of the metallic elements, the metallic elements other than the base element in the the first initial alloys being relatively non-reactive in the molten state.
  • non-reactive elements include Ni, Cr, Mo, W, V, Fe, Co, and Re.
  • suitable first initial alloys for carrying out the method of the invention are compositions which can be formed with sufficiently low oxygen and nitrogen levels.
  • Ni-Cr alloys can be maintained at about 20 ppm to levels up to about 30% chro­mium. No mechanism such as carbon deoxidation operates to remove nitrogen from Ni-Cr alloys, although, some dissociation occurs in vacuum resulting in nitrogen removal. Because nitrogen is re­moved by vaporization in accordance with Sievert's Law during melting to make the final high melting point alloy product, ni­trogen levels less than 50 ppm are acceptable in Ni-Cr initial alloys.
  • a binary 34% Ni-66% Ta initial alloy was formulated with elemental tantalum containing about 2200 ppm of oxygen, 100 ppm of nitrogen, and 600 ppm of carbon. Excess carbon was added during melting and the resultant 34% Ni-66% Ta initial alloy contained 357 ppm of oxygen, 16 ppm of nitrogen, and 300 pm of carbon. It has been found that the oxygen content in Ni-Ta alloys can be reduced without adding excess carbon by reducing the tantalum content of the alloy.
  • a binary 60% Ni-40% Ta alloy was found to contain only 15 ppm of oxygen, 4 ppm of nitrogen, and 300 ppm of carbon. It is believed that the decrease in the oxygen content is attribut­able to the inhibiting effect of tantalum on the carbon boil. At a level of approximately 40%, tantalum apparently does not inihibit the carbon boil.
  • the reduction of the oxygen content in Ni-Ta initial alloys without adding excess carbon is important because the carbon lev­els in the initial alloys must be low enough to meet the specifi­cations of the final high melting point alloy product.
  • the level of carbon specified is often less than 100 ppm.
  • Ni-Cb and Ni-V alloys can be re­duced in a similar manner as described above for Ni-Ta alloys.
  • Ni-V alloys have a high affinity for oxygen, however, and, conse­quently, the oxygen content can not be lowered in Ni-V alloys to the same extent it can be lowered in Ni-Ta and Ni-Cb alloys.
  • a 40% Ni-60% V alloy was formulated and found to contain 2900 ppm of oxygen and 300 ppm of nitrogen. By reducing the vanadium content to 42%, along with the addition of .12% carbon, the oxygen and nitrogen contents in the resultant 58% Ni-42% V alloy were lowered to 495 ppm and 223 ppm, respectively.
  • Figs. 1 and 2 are tables of suitable ini­tial alloys containing three to five elements for formulating equiax high melting point alloys.
  • Fig. 2 is a table listing suitable initial alloys containing as many as six elements for formulating complex single crystal high melting point alloys. The oxygen and nitrogen levels for each of the initial alloys in Figs. 1 and 2 fall within the permissible gas levels described above for practice of the invention.
  • At least one second initial alloy consisting essentially of the base element and at least one of the metallic elements, the metallic elements in the second initial alloys being relatively reactive in the molten state.
  • re­active elements include Ti, Al, Zr, Hf, Y, B, and rare earth ele­ments.
  • the second initial alloys set forth in the description which follows were formulated through a combination of vacuum induction melting and electron beam refining.
  • Ni-Al initial alloys were formulated and it was found that acceptable oxygen and nitrogen levels can be readily obtained.
  • Examples of the Ni-Al alloys formulated, and the gas levels obtained, are listed below: Ni(wt%) Al(wt%) O(ppm) N(ppm) C(wt%) 85 15 2 2 20 ppm 85 15 5 3 .04 88 12 4 4 50 ppm 90 10 4 4 .01 95 5 3 4 .02.
  • Ni-Ti initial alloys were formulated and it was found that the oxygen level in these alloys is high.
  • Examples of the Ni-Ti alloys formulated, and the gas levels obtained, are listed below: Ni(wt%) Ti(wt%) O(ppm) N(ppm) C(wt%) 75 25 600 8 .01 85 20 240 4 10 ppm 90 10 82 7 30 ppm 95 5 25 4 30 ppm.
  • Ni-Ti alloys due to the re­activity of titanium, the oxygen levels in Ni-Ti alloys are higher than for Ni-Al alloys. Because titanium has a strong affinity for carbon, a carbon boil is not effective in reducing the oxygen level in Ni-Ti alloys. Thus, for purposes of carrying out the method of the invention, only up to about 10% titanium may be included in Ni-Ti alloys. However, because the majority of cast high melting point alloys contain relatively low amounts of titanium, restricting titanium to about 10% in the second ini­tial alloys does not significantly limit the amount of initial alloys that can be used to make most high melting point alloy melts.
  • Fig. 3 is a three-dimensional graph showing the relationship between oxygen level and aluminum and titanium content in Ni-Al-Ti initial alloys. It appears that acceptable oxygen lev­els extend along the aluminum axis up to the range from about 5% to about 10% titanium. Thus, it is believed that the following alloys would be suitable second initial alloys for carrying out the method of the invention: Ni(wt%) Al(wt%) Ti(wt%) 20 80 0 40 60 0 15 76 5 38 57 5 17.3 72.7 10 35.5 54.5 10.
  • FIG. 4 is a table listing an example file of initial alloys which may be used in carrying out the method of the invention.
  • Figures 5-7 are tables showing sam­ple heat formulations for making various high melting point alloys using the example initial alloys shown in Fig. 4.
  • Fig. 5 shows a sample heat formulation for making HA-738 alloy.
  • a sample heat formulation for making 713C alloy is provided.
  • a sample heat formulation for making MAR-M-200+Hf alloy is listed in Fig. 7.
  • the selected amounts of the first and second initial alloys are melted to form a molten mixture having the predetermined composition of the high melting point alloy.
  • the first and second initial alloys may be charged in a vacuum induction furnace and simultaneously melted without any further refining steps. Because the first and second initial alloys have comparable melting points and the density disparities are much less than with elemental additions, the charge can be melted rapidly and homogenization is achieved in a relatively short period of time.
  • the molten mixture having the predetermined composition is solidified to form the final high melting point alloy product.
  • Those skilled in the art are familiar with suitable techniques for solidifying such molten mixtures.
  • a production size lot (2268 kg or 5000 lbs) of a single crystal high melting point alloy was made according to the method of the invention.
  • the specifications for the composition of the single crystal high melting point alloy that was formulated are as fol­lows: Ta: 11.75/12.25 wt%; Cr: 9.50/10.50 wt%; Al: 4.75/ 5.25 wt%; Co: 4.50/ 5.50 wt%; W: 3.75/ 4.25 wt%; Ti: 1.25/ 1.75 wt%; C: 50 ppm maximum; Ni: balance.
  • a first initial alloy comprised of the base element nickel and other non-reactive elements was formulated.
  • the composition of the first initial alloy was as follows: Ni(wt%) Cr(wt%) W(wt%) Ta(wt%) N(ppm) O(ppm) C(wt%) 39.30 19.70 7.80 22.90 8 91 .001.
  • the oxygen level of this alloy is above that nor­mally acceptable for first initial alloys, however, this alloy may still be used in the method of the invention.
  • the addition of about .02% to about 003% carbon could easily lower the oxygen level to less than 20 ppm.
  • a second initial alloy comprised of the base element nickel and other reactive elements was formulated.
  • the composition of the second initial alloy was as follows:
  • the resulting composition was within the specifications for the final high melting point alloy product and, therefore, no additional adjustments were required to reach the desired compo­sition. Furthermore, the levels of oxygen and nitrogen contained in the alloy were relatively low.
  • both the first and second initial alloys were separately filtered in the molten state in accordance with ultra-clean high melting point alloy casting practice. In addi­tion, the molten mixture of the first and second initial alloys was filtered after these alloys were melted together. Thus, the resultant high melting point alloy was, in effect, double fil­tered.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
EP88420277A 1987-08-07 1988-08-04 Verfahren zur Herstellung hochschmelzender Legierungen Withdrawn EP0302803A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US8257987A 1987-08-07 1987-08-07
US82579 1987-08-07

Publications (2)

Publication Number Publication Date
EP0302803A2 true EP0302803A2 (de) 1989-02-08
EP0302803A3 EP0302803A3 (de) 1989-10-18

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EP88420277A Withdrawn EP0302803A3 (de) 1987-08-07 1988-08-04 Verfahren zur Herstellung hochschmelzender Legierungen

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EP (1) EP0302803A3 (de)
JP (1) JPH01119634A (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2731017A1 (fr) * 1995-02-10 1996-08-30 Ald Vaccum Technologies Gmbh Procede de production d'alliages dans un creuset a paroi froide chauffe par induction
WO2005056846A1 (en) * 2003-12-02 2005-06-23 Worcester Polytechnic Institute Casting of aluminum based wrought alloys and aluminum based casting alloys
RU2453617C2 (ru) * 2009-06-04 2012-06-20 Сергей Фёдорович Павлов Способ пирометаллургической переработки окисленных никелевых руд
RU2470081C1 (ru) * 2011-05-05 2012-12-20 Открытое акционерное общество "Авиадвигатель" Способ получения литейных жаропрочных сплавов на никелевой основе
RU2672609C1 (ru) * 2017-12-29 2018-11-16 Акционерное общество "Металлургический завод "Электросталь" Способ восстановления и активации некондиционных отходов для сплавов на никелевой основе

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10041146B2 (en) 2014-11-05 2018-08-07 Companhia Brasileira de Metalurgia e Mineraçäo Processes for producing low nitrogen metallic chromium and chromium-containing alloys and the resulting products
US9771634B2 (en) * 2014-11-05 2017-09-26 Companhia Brasileira De Metalurgia E Mineração Processes for producing low nitrogen essentially nitride-free chromium and chromium plus niobium-containing nickel-based alloys and the resulting chromium and nickel-based alloys
RU2639396C1 (ru) * 2017-01-10 2017-12-21 Федеральное государственное бюджетное учреждение науки Институт металлургии Уральского отделения Российской академии наук (ИМЕТ УрО РАН) Способ пирометаллургической переработки окисленной никелевой руды

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3620719A (en) * 1969-11-12 1971-11-16 Trw Inc Method of vacuum refining high-temperature alloys
US4119458A (en) * 1977-11-14 1978-10-10 General Electric Company Method of forming a superalloy
FR2512068A1 (fr) * 1981-09-01 1983-03-04 Sofrem Procede d'introduction d'elements d'addition a point de fusion eleve dans des metaux et alliages en fusion tels que fontes et aciers
US4718940A (en) * 1986-05-05 1988-01-12 Mcphillips Kerry A Method of manufacturing alloy for use in fabricating metal parts

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3620719A (en) * 1969-11-12 1971-11-16 Trw Inc Method of vacuum refining high-temperature alloys
US4119458A (en) * 1977-11-14 1978-10-10 General Electric Company Method of forming a superalloy
FR2512068A1 (fr) * 1981-09-01 1983-03-04 Sofrem Procede d'introduction d'elements d'addition a point de fusion eleve dans des metaux et alliages en fusion tels que fontes et aciers
US4718940A (en) * 1986-05-05 1988-01-12 Mcphillips Kerry A Method of manufacturing alloy for use in fabricating metal parts

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2731017A1 (fr) * 1995-02-10 1996-08-30 Ald Vaccum Technologies Gmbh Procede de production d'alliages dans un creuset a paroi froide chauffe par induction
WO2005056846A1 (en) * 2003-12-02 2005-06-23 Worcester Polytechnic Institute Casting of aluminum based wrought alloys and aluminum based casting alloys
US7201210B2 (en) 2003-12-02 2007-04-10 Worcester Polytechnic Institute Casting of aluminum based wrought alloys and aluminum based casting alloys
RU2453617C2 (ru) * 2009-06-04 2012-06-20 Сергей Фёдорович Павлов Способ пирометаллургической переработки окисленных никелевых руд
RU2470081C1 (ru) * 2011-05-05 2012-12-20 Открытое акционерное общество "Авиадвигатель" Способ получения литейных жаропрочных сплавов на никелевой основе
RU2672609C1 (ru) * 2017-12-29 2018-11-16 Акционерное общество "Металлургический завод "Электросталь" Способ восстановления и активации некондиционных отходов для сплавов на никелевой основе

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Publication number Publication date
EP0302803A3 (de) 1989-10-18
JPH01119634A (ja) 1989-05-11

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