US3432369A - Method of making magnetically anisotropic permanent magnets - Google Patents

Method of making magnetically anisotropic permanent magnets Download PDF

Info

Publication number
US3432369A
US3432369A US549029A US3432369DA US3432369A US 3432369 A US3432369 A US 3432369A US 549029 A US549029 A US 549029A US 3432369D A US3432369D A US 3432369DA US 3432369 A US3432369 A US 3432369A
Authority
US
United States
Prior art keywords
melt
alloy
seed
oriented
axially
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US549029A
Other languages
English (en)
Inventor
Pieter Aarat Naastepad
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Philips North America LLC
US Philips Corp
Original Assignee
US Philips Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by US Philips Corp filed Critical US Philips Corp
Application granted granted Critical
Publication of US3432369A publication Critical patent/US3432369A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt
    • 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
    • C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
    • C22C38/105—Ferrous alloys, e.g. steel alloys containing cobalt containing Co and Ni
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/52—Alloys

Definitions

  • the invention relates to a method of manufacturing rod-shaped magnetically anisotropic permanent magnet bodies having a cubic crystal structure and a (100) direction of the crystals which is substantially axially oriented from an alloy containing, in addition to, Fe and the normally present impurities, 16-42% of Co, 7-20% of Ni, 6-11% of- Al, 010% of Cu, 110% of Ti, 0-4% of Nb, 08% of Ta, 0l% of Si, 01% of S, a melt of the said alloy being cooled in a temperature gradient.
  • Normally-present impurities are to be understood to mean herein those impurities which are already present in the raw materials. In general they total approximately 0.5%.
  • alloys in the aforesaid range which contain given quantities of Co and Ti may show very high coercive forces, (up to 2000 oersted)
  • Further means are provided to avoid heat flowing away to an undesired extent in a lateral direction, for example, additional heat. It is possible in this manner to obtain a (BH) value of 5.5 10 g.0., which is reproducible in mass production.
  • this method consists in that the molten alloy is continuously applied to the top of a vertically arranged pipe, the rod of the molten alloy being continuusly, or discontinuously, drawn out of the pipe on the lower side.
  • the desired crystal orientation in axial direction is obtained by withdrawing the heat through the rod itself in one direction-the longitudinal direction of the rodwhich can even be promoted by additionally cooling the part of the rod emerging out of the pipe.
  • the pipe be insulated in a transverse direction and/ or heated by additional means so as to check the thermal losses.
  • magnets without crystal orientation can be mass produced which show high coercive forces of 1000 0e. and more in a reproducible manner.
  • a very good representative of this group is, for example, the alloy consisting of 34% of Co, 14.5% of Ni, 7% of A1, 4.5% of Cu, 5% of Ti, rest Fe and the impurities normally present. With this alloy magnets can be mass-produced without crystal orientation having (BH) values of 4-5 10 go. and coercive forces of 1300-1500 oe.
  • Another object of the invention is to provide a method of manufacturing anisotropic permanent magnets consisting of a Co-Ni-Al-Me alloy having a (BH) value of at least 9.0 l g.o.
  • the invention is based on the discovery that in order to obtain magnetically anisotropic permanent magnets having a high (BH) value and a high coercive force from the aforesaid group of alloys, the conditions at the solidification front, or points at which solidification of the melt occurs, must be optimum. In addition to the withdrawal of heat in the axial direction, additional measures must be taken to insure formation of the desired crystal orientation, a criterion for which is that the (BH),,,,,,, value must be at least 9X 10 gauss-oersted. Thus, it has been found that the solidification rate R must meet special requirements dependent upon the composition of the alloy and dependent upon quantities determined by the apparatus used.
  • the solidification rate R (mm/min.) for a given Ti-content, a given temperature gradient G C/mm.) then is kept below a given maximum value.
  • the temperature gradient adjusts in a particular oven, the temperature gradient at the solidification front in the melt-which, ultimately, is decisive of the product to be manufacturedwill differ considerably from the first mentioned gradient. This difference is determined principally by the rate R with which the solidification front moves so that this rate R is the most important variable quantity.
  • the solidification of the alloy begin after the melt has been contacted with a seed which has a dendritically formed boundary surface oriented in the direction.
  • a seed for example, a cubic monocrystal of an alloy of the composition: 23% of Co, 14% of Ni, 3% of Cu, 8% of Al, and the balance Fe, may be used.
  • Such an alloy is also known in the trade at Ticonal G/G.
  • the oxide skin which is always present on the surface of such a melt (both of a partially molten seed and on the molten alloy to be contacted therewith) must be removed.
  • This oxide skin between the seed and the melt may be removed by means of cryolite (Na AIF which can be provided on the boundary surface of the seed before the melt and the seed are contacted with one another.
  • cryolite Na AIF which can be provided on the boundary surface of the seed before the melt and the seed are contacted with one another.
  • the oxide skin may also be removed mechanically. This may be done, for example, with a stirring rod.
  • the skin can be removed by convection flows in the melt, but convection flows only will be sufiiciently operative when the diameter of the melt is large 10 mm.). The skin may be forced upwards by said flows.
  • Example I A rod, 2 cm. long, 20 mm. diameter, of an alloy having the composition:
  • a layer of cryolite was provided on the boundary surface between the seed and the rod.
  • a ceramic pipe was slid over the rod and the seat, after which the assembly was placed in a vertical oven.
  • the rod was melted in an atmosphere of cleaned argon gas.
  • the position of the pipe in the oven was chosen to be such that part of the oriented seed also melts.
  • the rate R was 0.15 mm./min.
  • Example IV A rod, diameter 20 mm., of an alloy having the composition:
  • the rate R was 2 mm./ min.
  • a method of manufacturing rod-shaped magnetically anisotropic permanent magnet bodies having a cubic crystal structure and a (100) direction of the crystals oriented substantially axially from an alloy consisting of 16-42% of Co, 720% of Ni, 611% of Al, 010% of Cu, 1-10% of Ti, 04% of Nb, 0-8% of Ta, 0l% of Si, 01% of S and the balance principally Fe comprising the steps of forming a melt of the said alloy, contacting the melt with an oxide-free seed having a cubic crystal structure, the (100) direction of which is oriented axially and which is miscible in the liquid phase of the melt, the seed during contact with the melt partially melting and forming a dendritic boundary surface with an axially oriented 100) direction of the crystal, and cooling the melt at a predetermined solidification rate R (mm./min.), which for a given temperature gradient G C./min.) at the solidification front is kept below a predetermined maximum value, which increases as the Ticontent decreases, where

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Power Engineering (AREA)
  • Hard Magnetic Materials (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
US549029A 1965-06-09 1966-05-10 Method of making magnetically anisotropic permanent magnets Expired - Lifetime US3432369A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
NL656507303A NL151831B (nl) 1965-06-09 1965-06-09 Werkwijze voor de vervaardiging van staafvormige, magnetisch anisotrope, permanente magneetlichamen met kubische kristalstructuur en een voornamelijk axiaal georienteerde (100)-richting van de kristallen.

Publications (1)

Publication Number Publication Date
US3432369A true US3432369A (en) 1969-03-11

Family

ID=19793332

Family Applications (1)

Application Number Title Priority Date Filing Date
US549029A Expired - Lifetime US3432369A (en) 1965-06-09 1966-05-10 Method of making magnetically anisotropic permanent magnets

Country Status (10)

Country Link
US (1) US3432369A (enrdf_load_stackoverflow)
AT (1) AT273513B (enrdf_load_stackoverflow)
BE (1) BE682208A (enrdf_load_stackoverflow)
CH (1) CH488257A (enrdf_load_stackoverflow)
DE (1) DE1533335C3 (enrdf_load_stackoverflow)
DK (1) DK119470B (enrdf_load_stackoverflow)
ES (1) ES327640A1 (enrdf_load_stackoverflow)
GB (1) GB1095846A (enrdf_load_stackoverflow)
NL (1) NL151831B (enrdf_load_stackoverflow)
SE (1) SE331317B (enrdf_load_stackoverflow)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3908737A (en) * 1973-07-31 1975-09-30 Nippon Steel Corp Method for producing grain-oriented electrical steel sheet utilizing a continuous casting process
US4007065A (en) * 1975-02-28 1977-02-08 Arnold Engineering Company Hysteresis alloy
US4134756A (en) * 1976-09-07 1979-01-16 Hitachi Metals, Ltd. Permanent magnet alloys
US4784703A (en) * 1983-08-26 1988-11-15 Grumman Aerospace Corporation Directional solidification and densification of permanent magnets having single domain size MnBi particles
US10109418B2 (en) 2013-05-03 2018-10-23 Battelle Memorial Institute System and process for friction consolidation fabrication of permanent magnets and other extrusion and non-extrusion structures
US10189063B2 (en) 2013-03-22 2019-01-29 Battelle Memorial Institute System and process for formation of extrusion products
US10695811B2 (en) 2013-03-22 2020-06-30 Battelle Memorial Institute Functionally graded coatings and claddings
US11045851B2 (en) 2013-03-22 2021-06-29 Battelle Memorial Institute Method for Forming Hollow Profile Non-Circular Extrusions Using Shear Assisted Processing and Extrusion (ShAPE)
US11383280B2 (en) 2013-03-22 2022-07-12 Battelle Memorial Institute Devices and methods for performing shear-assisted extrusion, extrusion feedstocks, extrusion processes, and methods for preparing metal sheets
US11549532B1 (en) 2019-09-06 2023-01-10 Battelle Memorial Institute Assemblies, riveted assemblies, methods for affixing substrates, and methods for mixing materials to form a metallurgical bond
US11919061B2 (en) 2021-09-15 2024-03-05 Battelle Memorial Institute Shear-assisted extrusion assemblies and methods
US12186791B2 (en) 2013-03-22 2025-01-07 Battelle Memorial Institute Devices and methods for performing shear-assisted extrusion and extrusion processes
US12358035B2 (en) 2013-03-22 2025-07-15 Battelle Memorial Institute Devices and methods for performing shear-assisted extrusion and extrusion processes
US12365027B2 (en) 2013-03-22 2025-07-22 Battelle Memorial Institute High speed shear-assisted extrusion
US12403516B2 (en) 2020-09-28 2025-09-02 Battelle Memorial Institute Shape processes, feedstock materials, conductive materials and/or assemblies

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4289570A (en) * 1978-12-13 1981-09-15 United Technologies Corporation Seed and method for epitaxial solidification
RU2127774C1 (ru) * 1997-01-28 1999-03-20 Акционерное общество открытого типа Научно-производственное объединение "Магнетон" Способ получения высококачественных монокристаллических заготовок

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2673310A (en) * 1949-09-07 1954-03-23 Deutsche Edelstahlwerke Ag Permanent magnet
US2837452A (en) * 1955-01-19 1958-06-03 Philips Corp Method of making anisotropic permanent magnets
US2862287A (en) * 1952-12-17 1958-12-02 Philips Corp Method of making cast alnico magnets
US2933427A (en) * 1956-03-28 1960-04-19 Philips Corp Permanent anisotropic magnet and method of making same
US3085036A (en) * 1960-03-11 1963-04-09 Ct Magneti Permanenti Monocrystalline permanent magnets and method of making them
US3175901A (en) * 1962-02-07 1965-03-30 U S Magnet & Alloy Corp Permanent magnet and alloy therefor
US3206337A (en) * 1961-11-08 1965-09-14 Hamilton Watch Co Cobalt-platinum alloy and magnets made therefrom
US3314828A (en) * 1964-01-22 1967-04-18 Swift Levick & Sons Ltd Permanent magnets
US3350240A (en) * 1963-07-05 1967-10-31 Sumitomo Spec Metals Method of producing magnetically anisotropic single-crystal magnets

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2673310A (en) * 1949-09-07 1954-03-23 Deutsche Edelstahlwerke Ag Permanent magnet
US2862287A (en) * 1952-12-17 1958-12-02 Philips Corp Method of making cast alnico magnets
US2837452A (en) * 1955-01-19 1958-06-03 Philips Corp Method of making anisotropic permanent magnets
US2933427A (en) * 1956-03-28 1960-04-19 Philips Corp Permanent anisotropic magnet and method of making same
US3085036A (en) * 1960-03-11 1963-04-09 Ct Magneti Permanenti Monocrystalline permanent magnets and method of making them
US3206337A (en) * 1961-11-08 1965-09-14 Hamilton Watch Co Cobalt-platinum alloy and magnets made therefrom
US3175901A (en) * 1962-02-07 1965-03-30 U S Magnet & Alloy Corp Permanent magnet and alloy therefor
US3350240A (en) * 1963-07-05 1967-10-31 Sumitomo Spec Metals Method of producing magnetically anisotropic single-crystal magnets
US3314828A (en) * 1964-01-22 1967-04-18 Swift Levick & Sons Ltd Permanent magnets

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3908737A (en) * 1973-07-31 1975-09-30 Nippon Steel Corp Method for producing grain-oriented electrical steel sheet utilizing a continuous casting process
US4007065A (en) * 1975-02-28 1977-02-08 Arnold Engineering Company Hysteresis alloy
US4134756A (en) * 1976-09-07 1979-01-16 Hitachi Metals, Ltd. Permanent magnet alloys
US4784703A (en) * 1983-08-26 1988-11-15 Grumman Aerospace Corporation Directional solidification and densification of permanent magnets having single domain size MnBi particles
US11534811B2 (en) 2013-03-22 2022-12-27 Battelle Memorial Institute Method for forming hollow profile non-circular extrusions using shear assisted processing and extrusion (ShAPE)
US12358035B2 (en) 2013-03-22 2025-07-15 Battelle Memorial Institute Devices and methods for performing shear-assisted extrusion and extrusion processes
US10695811B2 (en) 2013-03-22 2020-06-30 Battelle Memorial Institute Functionally graded coatings and claddings
US11045851B2 (en) 2013-03-22 2021-06-29 Battelle Memorial Institute Method for Forming Hollow Profile Non-Circular Extrusions Using Shear Assisted Processing and Extrusion (ShAPE)
US11383280B2 (en) 2013-03-22 2022-07-12 Battelle Memorial Institute Devices and methods for performing shear-assisted extrusion, extrusion feedstocks, extrusion processes, and methods for preparing metal sheets
US11517952B2 (en) 2013-03-22 2022-12-06 Battelle Memorial Institute Shear assisted extrusion process
US12377455B2 (en) 2013-03-22 2025-08-05 Battelle Memorial Institute Functionally graded coatings and claddings
US12365027B2 (en) 2013-03-22 2025-07-22 Battelle Memorial Institute High speed shear-assisted extrusion
US11684959B2 (en) 2013-03-22 2023-06-27 Battelle Memorial Institute Extrusion processes for forming extrusions of a desired composition from a feedstock
US10189063B2 (en) 2013-03-22 2019-01-29 Battelle Memorial Institute System and process for formation of extrusion products
US12337366B2 (en) 2013-03-22 2025-06-24 Battelle Memorial Institute Devices and methods for performing shear-assisted extrusion, extrusion feedstocks, extrusion processes, and methods for preparing metal sheets
US12186791B2 (en) 2013-03-22 2025-01-07 Battelle Memorial Institute Devices and methods for performing shear-assisted extrusion and extrusion processes
US10109418B2 (en) 2013-05-03 2018-10-23 Battelle Memorial Institute System and process for friction consolidation fabrication of permanent magnets and other extrusion and non-extrusion structures
US11946504B2 (en) 2019-09-06 2024-04-02 Battelle Memorial Institute Assemblies, riveted assemblies, methods for affixing substrates, and methods for mixing materials to form a metallurgical bond
US11549532B1 (en) 2019-09-06 2023-01-10 Battelle Memorial Institute Assemblies, riveted assemblies, methods for affixing substrates, and methods for mixing materials to form a metallurgical bond
US12403516B2 (en) 2020-09-28 2025-09-02 Battelle Memorial Institute Shape processes, feedstock materials, conductive materials and/or assemblies
US11919061B2 (en) 2021-09-15 2024-03-05 Battelle Memorial Institute Shear-assisted extrusion assemblies and methods
US12397334B2 (en) 2021-09-15 2025-08-26 Battelle Memorial Institute Shear-assisted extrusion assemblies and methods

Also Published As

Publication number Publication date
NL151831B (nl) 1976-12-15
CH488257A (de) 1970-03-31
NL6507303A (enrdf_load_stackoverflow) 1966-12-12
GB1095846A (en) 1967-12-20
SE331317B (enrdf_load_stackoverflow) 1970-12-21
BE682208A (enrdf_load_stackoverflow) 1966-12-07
DE1533335C3 (de) 1974-10-10
AT273513B (de) 1969-08-11
ES327640A1 (es) 1967-07-16
DK119470B (da) 1971-01-11
DE1533335B2 (de) 1974-03-07
DE1533335A1 (de) 1969-12-18

Similar Documents

Publication Publication Date Title
US3432369A (en) Method of making magnetically anisotropic permanent magnets
JP2011080152A (ja) 高弾性限を有する非晶質合金の成形品を形成する方法
GB2112309A (en) Making a cast single crystal article
JPS62109946A (ja) 希土類・鉄合金から磁歪ロツドを製造する方法
US20060086476A1 (en) Investment casting of bulk-solidifying amorphous alloys
US4202400A (en) Directional solidification furnace
CN103343238A (zh) 一种用于易挥发元素合金的区域熔化定向凝固方法
US5067551A (en) Method for manufacturing alloy rod having giant magnetostriction
JPH01123021A (ja) 希土類金属−鉄合金棒の磁気歪応答を増大するための熱処理方法
US3529958A (en) Method for the formation of an alloy composed of metals reactive in their elemental form with a melting container
US3189957A (en) Method of manufacturing permanent magnets by continuous castings
US4186046A (en) Growing doped single crystal ceramic materials
JPH049629B2 (enrdf_load_stackoverflow)
US3434892A (en) Directionally solidified permanent magnet alloys with aligned ferro-magnetic whiskers
US4342608A (en) Mn-Al Permanent magnets and their manufacture
JPS627839A (ja) ＮｉＴｉ系合金の製造方法
US3261722A (en) Process for preparing semiconductor ingots within a depression
US4396441A (en) Permanent magnet having ultra-high coercive force and large maximum energy product and method of producing the same
US2990261A (en) Processing of boron compact
US3234609A (en) Method of making magnetically anisotropic permanent magnets
US3783032A (en) Method for producing directionally solidified nickel base alloy
US4946746A (en) Novel metal fiber and process for producing the same
US5236033A (en) Method for producing a body from a material susceptible to thermal cracking and casting mold for executing the method
US2804415A (en) Preparation of mnbi bodies
US3428498A (en) Preparation of sintered permanent alnico magnets