US3546030A - Permanent magnets built up of m5r - Google Patents

Permanent magnets built up of m5r Download PDF

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US3546030A
US3546030A US644101A US3546030DA US3546030A US 3546030 A US3546030 A US 3546030A US 644101 A US644101 A US 644101A US 3546030D A US3546030D A US 3546030DA US 3546030 A US3546030 A US 3546030A
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compounds
elements
combination
permanent magnets
compound
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US644101A
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Kurt Heinz Jurgen Buschow
Wilhelmus Antonius Johan Velge
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US Philips Corp
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032Magnets 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
    • H01F1/04Magnets 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
    • H01F1/047Alloys characterised by their composition
    • H01F1/053Alloys characterised by their composition containing rare earth metals
    • H01F1/055Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/0555Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together
    • H01F1/0557Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together sintered
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C28/00Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper

Definitions

  • the component of these particles which is essential to these properties is M R, Where M is either Co or a combination of Co with one or more of the elements Fe, Cu, Ni and where R is either La, Th, or a combination of Th with one or more of the elements of the rare earths, or a combination of at least three elements of the rare earths.
  • the present invention is based upon the discovery that in compounds Co R having a similar structure to that of Co Y, the said combination of magnetic properties which causes the compound to be a good raw material for the manufacture of permanent magnets (high uniaxial aniso tropy combined with high saturation magnetization) is obtainable if two conditions are fulfilled With regard to the electron structure of the relevant compound.
  • the first condition is generally fulfilled by choosing for R those elements which can form with Co compounds of the relevant structure and which occur as trivalent ions in these compounds. Furthermore Th, Ce and Yb, as well as certain combinations of elements, appear to satisfy the first condition.
  • the second condition is fulfilled by choosing for R those elements or combinations of elements the total magnetic moments of which are directed in parallel with those of the Co-ions or which do not contribute to the magnetic moment.
  • M instead of the above-mentioned Co, a combination of Co with one or more of the elements Fe, Ni, Cu.
  • the compounds in which M is such a combination generally have a lower sensitivity to deformation of the coercive force and the saturation magnetization.
  • Fe, or Ni, Co or a combination can be substituted for M while retaining favorable magnetic properties depends upon R and the substituents which have been chosen. Thus it has been found, for example, that if R is La and M is a combination of Co and Fe, no more than 5 at. precent of Fe may be present, Whereas the maximum content of Fe may be at. percent if R is Th. If the Fe-content exceeds the specified percentages, the examples given no longer have the hexagonal structure required, resulting in an abrupt decline in magnetic properties. However, in other examples, the magnetic properties may decline gradually, starting from a certain atomic percentage of the substituent.
  • the invention also relates to a method of manufacturing a permanent magnet as above described.
  • a body is first manufactured by melting the component elements to form the compound of R and subsequently cooling the mass.
  • the body is homogenized by annealing in an atmosphere which protects against oxidizing influences, at a temperature which lies as nearly as possible, i.e., immediately, below the melting point.
  • the body is subsequently cooled to room temperature and pulverized.
  • the powder possibly after annealing, then is formed into a magnetic body by molding, possibly in a magnetic field.
  • the homogenization is followed by cooling to room temperature. This cooling may take place at a low rate if no undesired phases occur during this process. If, however, this should be the case, then in one form of the method according to the invention the body should be quenched to room temperature after homogenization.
  • the quenching process affords the additional advantage that the body becomes more brittle and this is advantageous with a view to the subsequent pulverization.
  • the maximum energy product (BH) has been measured on a permanent magnet made from CO La Ce Sm and is 5x10 GausS-OerSted.
  • a permanent magnet constituted of fine particles, and having magnetic properties, said particles having as a component which is essential to these properties the compound M R, having a hexagonal crystal structure where M is selected from the group consisting of Co and a combination of Co with at least one element selected from the group consisting of Fe, Cu, Ni and where R is selected from the group consisting of La, Th a combination of about 50% La, about 25% Ce and about 25% Sin, and a combination of Th with up to two of the rare earth elements.

Description

United States Patent Ofi ice 3,546,030 Patented Dec. 8, 1970 3,546,030 PERMANENT MAGNETS BUILT UP F M R Kurt Heinz Jurgen Buschow and Wilhelmus Antonius Johannes Josephus Velge, Emmasingel, Eindhoven,
Netherlands, assignors, by mesne assignments, to U.S. Philips Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed June 7, 1967, Ser. No. 644,101 Claims priority, application Netherlands, June 16, 1966, 6608335 Int. Cl. H01f 1/08; C22c 19/00, 31/02 U.S. Cl. 148--31.57 5 Claims ABSTRACT OF THE DISCLOSURE This invention relates to permanent magnets constituted of fine particles having in themselves permanent magnetic properties. The component of these particles which is essential to these properties is M R, Where M is either Co or a combination of Co with one or more of the elements Fe, Cu, Ni and where R is either La, Th, or a combination of Th with one or more of the elements of the rare earths, or a combination of at least three elements of the rare earths.
Others have measured the magnetic properties of numerous intermetallic compounds of the stoichiometric composition M R. Thus for example, many compounds of the from Co -Z have been examined, where Z is an element of the rare earths which are regarded also to include Y. Of these compounds, the magnetic moments and the temperature dependence of the saturation moments have been measured. Further, the magnetic properties of the compounds Co CnTb, Co NiDy, CdYCo and GdNdCo were determined. All these compounds have a hexagonal structure of the CaCu type.
The present invention is based upon the discovery that in compounds Co R having a similar structure to that of Co Y, the said combination of magnetic properties which causes the compound to be a good raw material for the manufacture of permanent magnets (high uniaxial aniso tropy combined with high saturation magnetization) is obtainable if two conditions are fulfilled With regard to the electron structure of the relevant compound.
First the geometry of the electrons in the Co-ions as compared with that in the compound Co Y must not be essentially changed by R, that is to say the population of the 3-d shell in the Co-ion remain substantially the same.
Secondly, the total magnetic moment of the compound which is built up of contributions of both Co and R must not be detnmentally affected by the contribution of R.
The first condition is generally fulfilled by choosing for R those elements which can form with Co compounds of the relevant structure and which occur as trivalent ions in these compounds. Furthermore Th, Ce and Yb, as well as certain combinations of elements, appear to satisfy the first condition.
The second condition is fulfilled by choosing for R those elements or combinations of elements the total magnetic moments of which are directed in parallel with those of the Co-ions or which do not contribute to the magnetic moment.
When the two conditions are combined there appears to exist for R, in addition to the known elements and combinations of elements, a large number of substitution possibilities. Experiments have shown that of these manifold suitable substitutions for R, only the following elements and combinations of elements with Co can form a compound Co R which can be used with good result (sufliciently high H and (BH) as a raw material for the manufacture of permanent magnets: La, Th, or a combination of Th with one or more of the elements of the rare earths, or combinations of at least three rare earths.
It is possible in these compounds to choose for M, instead of the above-mentioned Co, a combination of Co with one or more of the elements Fe, Ni, Cu. The compounds in which M is such a combination generally have a lower sensitivity to deformation of the coercive force and the saturation magnetization.
The extent to which Fe, or Ni, Co or a combination can be substituted for M while retaining favorable magnetic properties depends upon R and the substituents which have been chosen. Thus it has been found, for example, that if R is La and M is a combination of Co and Fe, no more than 5 at. precent of Fe may be present, Whereas the maximum content of Fe may be at. percent if R is Th. If the Fe-content exceeds the specified percentages, the examples given no longer have the hexagonal structure required, resulting in an abrupt decline in magnetic properties. However, in other examples, the magnetic properties may decline gradually, starting from a certain atomic percentage of the substituent.
The compounds Co La, Co La Sm Th and C0 La Ce Sm for example, satisfy the abovementioned conditions.
The invention also relates to a method of manufacturing a permanent magnet as above described. In this method, a body is first manufactured by melting the component elements to form the compound of R and subsequently cooling the mass. The body is homogenized by annealing in an atmosphere which protects against oxidizing influences, at a temperature which lies as nearly as possible, i.e., immediately, below the melting point. The body is subsequently cooled to room temperature and pulverized. The powder, possibly after annealing, then is formed into a magnetic body by molding, possibly in a magnetic field.
Compounds of the formula M R generally have an incongment melting point. As a result, compounds of R and M other than M R may also occur during solidification. During the annealing of the molding at a temperature which lies just below the melting temperature, all the compounds formed during solidification will be converted into the compound M R, that is to say are homogenized. The temperature is chosen therefore at a maximum inter alia to give the particles the greater possible mobility, which enhances an efficient conversion of other compounds into M R.
The homogenization is followed by cooling to room temperature. This cooling may take place at a low rate if no undesired phases occur during this process. If, however, this should be the case, then in one form of the method according to the invention the body should be quenched to room temperature after homogenization.
The quenching process affords the additional advantage that the body becomes more brittle and this is advantageous with a view to the subsequent pulverization.
The invention may be explained more fully with reference to magnetic properties measured on the following examples of compounds (M R particles) according to the invention all which were made in the aforesaid manner:
The maximum energy product (BH) has been measured on a permanent magnet made from CO La Ce Sm and is 5x10 GausS-OerSted.
What is claimed is:
1. A permanent magnet constituted of fine particles, and having magnetic properties, said particles having as a component which is essential to these properties the compound M R, having a hexagonal crystal structure where M is selected from the group consisting of Co and a combination of Co with at least one element selected from the group consisting of Fe, Cu, Ni and where R is selected from the group consisting of La, Th a combination of about 50% La, about 25% Ce and about 25% Sin, and a combination of Th with up to two of the rare earth elements.
2. A permanent magnet as claimed in claim 1 in which R is a combination of Th and two rare earth elements.
3. A permanent magnet as claimed in claim 1 in which M is Co and R is La.
4. A permanent magnet as claimed in claim 2 in which M is Co and R is La Sm Th 5. A permanent magnet as claimed in claim 1 in which M is Co and R is La Ce Sm References Cited UNITED STATES PATENTS 2,813,789 11/1957 Glaser 123 3,102,0U2 871963 WalIaceet al. 'L. 75 1'52X 3,326,637 6/1967 Holtzberg et al. 75152X 3,342,591 9/1967 Gambino et al. 75152 3,421,889 1/1969 Ostertag et a1 75170 3,424,578 1/1969 Strnat et al. 75213 L. DEWAYNE RUTLEDGE, Primary Examiner G. K. WHITE, Assistant Examiner U.S. Cl. X.R.
US644101A 1966-06-16 1967-06-07 Permanent magnets built up of m5r Expired - Lifetime US3546030A (en)

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AT (1) AT286657B (en)
BE (1) BE700002A (en)
CH (1) CH499857A (en)
DE (1) DE1558550B2 (en)
DK (1) DK117970B (en)
ES (1) ES341762A1 (en)
GB (1) GB1187853A (en)
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SE (1) SE332866B (en)

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2003749A1 (en) * 1969-01-24 1970-07-30 Philips Nv Hydrides with the formula ABnHm
US3652343A (en) * 1970-09-14 1972-03-28 Gen Electric Permanent magnet material powders having superior magnetic characteristics
US3655463A (en) * 1970-04-30 1972-04-11 Gen Electric Sintered cobalt-rare earth intermetallic process using solid sintering additive
US3655464A (en) * 1970-04-30 1972-04-11 Gen Electric Process of preparing a liquid sintered cobalt-rare earth intermetallic product
US3664892A (en) * 1968-01-31 1972-05-23 Gen Electric Permanent magnet material powders having superior magnetic characteristics
US3755007A (en) * 1971-04-01 1973-08-28 Gen Electric Stabilized permanent magnet comprising a sintered and quenched body of compacted cobalt-rare earth particles
US3790414A (en) * 1967-11-15 1974-02-05 Matsushita Electric Ind Co Ltd As-CAST, RARE-EARTH-Co-Cu PERMANENT MAGNET MATERIAL
US3839102A (en) * 1967-11-15 1974-10-01 Matsushita Electric Ind Co Ltd Permanent magnet
US3844850A (en) * 1972-04-17 1974-10-29 Gen Electric Large grain cobalt-samarium intermetallic permanent magnet material and process
US3856579A (en) * 1972-12-04 1974-12-24 Battelle Development Corp Sputtered magnetic materials comprising rare-earth metals and method of preparation
US3905839A (en) * 1971-12-17 1975-09-16 Gen Electric Liquid sintered cobalt-rare earth intermetallic product
US3905840A (en) * 1972-06-15 1975-09-16 Gen Electric Sintered cobalt-rare earth intermetallic product
US3919003A (en) * 1971-12-17 1975-11-11 Gen Electric Sintered cobalt-rare earth intermetallic product
US3919004A (en) * 1970-04-30 1975-11-11 Gen Electric Liquid sintered cobalt-rare earth intermetallic product
US3947295A (en) * 1973-02-09 1976-03-30 Matsushita Electric Industrial Co., Ltd. Hard magnetic material
US3956031A (en) * 1969-12-24 1976-05-11 Texas Instruments Incorporated Magnetic materials and the formation thereof
US3997371A (en) * 1973-11-12 1976-12-14 Hitachi Metals, Ltd. Permanent magnet
US4002508A (en) * 1974-08-27 1977-01-11 Aimants Ugimag S.A. Composition for permanent magnets of the family "rare earths-transition metals" and process for producing such a magnet
US4003767A (en) * 1971-12-27 1977-01-18 Bbc Brown Boveri & Company Limited Procedure for the production of permanent magnetic sinter bodies using a ternary cobalt-lanthanoid compound
US4075042A (en) * 1973-11-16 1978-02-21 Raytheon Company Samarium-cobalt magnet with grain growth inhibited SmCo5 crystals
US4210471A (en) * 1976-02-10 1980-07-01 Tdk Electronics, Co., Ltd. Permanent magnet material and process for producing the same
US4213803A (en) * 1976-08-31 1980-07-22 Tdk Electronics Company Limited R2 Co17 Rare type-earth-cobalt, permanent magnet material and process for producing the same
US4370296A (en) * 1978-03-21 1983-01-25 Fdx Associates, L.P. Toroidal fusion reactor having ohmic heating coil substantially adjacent toroidal fusion region
US4370295A (en) * 1978-03-21 1983-01-25 Fdx Associates, L.P. Fusion-fission power generating device having fissile-fertile material within the region of the toroidal field coils generating means
US4382061A (en) * 1980-10-25 1983-05-03 Th. Goldschmidt Ag Alloy preparation for permanent magnets
US4536233A (en) * 1980-12-16 1985-08-20 Kabushiki Kaisha Suwa Seikosha Columnar crystal permanent magnet and method of preparation
US4710242A (en) * 1980-08-11 1987-12-01 Fujitsu Limited Material for temperature sensitive elements
US5382303A (en) * 1992-04-13 1995-01-17 Sps Technologies, Inc. Permanent magnets and methods for their fabrication

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3625779A (en) * 1969-08-21 1971-12-07 Gen Electric Reduction-fusion process for the production of rare earth intermetallic compounds
JPS52115000A (en) * 1976-03-22 1977-09-27 Tdk Corp Material of permanent magnet

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2813789A (en) * 1952-04-08 1957-11-19 Glaser Louis Permanent magnet alloys
US3102002A (en) * 1960-03-25 1963-08-27 Univ Pittsburgh Ferromagnetic materials prepared from lanthanons and transition metals
US3326637A (en) * 1963-12-27 1967-06-20 Ibm Ferromagnetic intermetallic compounds and method of preparation
US3342591A (en) * 1964-08-31 1967-09-19 Ibm Ferromagnetic compounds and method of preparation
US3421889A (en) * 1966-01-13 1969-01-14 Us Air Force Magnetic rare earth-cobalt alloys
US3424578A (en) * 1967-06-05 1969-01-28 Us Air Force Method of producing permanent magnets of rare earth metals containing co,or mixtures of co,fe and mn

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2813789A (en) * 1952-04-08 1957-11-19 Glaser Louis Permanent magnet alloys
US3102002A (en) * 1960-03-25 1963-08-27 Univ Pittsburgh Ferromagnetic materials prepared from lanthanons and transition metals
US3326637A (en) * 1963-12-27 1967-06-20 Ibm Ferromagnetic intermetallic compounds and method of preparation
US3342591A (en) * 1964-08-31 1967-09-19 Ibm Ferromagnetic compounds and method of preparation
US3421889A (en) * 1966-01-13 1969-01-14 Us Air Force Magnetic rare earth-cobalt alloys
US3424578A (en) * 1967-06-05 1969-01-28 Us Air Force Method of producing permanent magnets of rare earth metals containing co,or mixtures of co,fe and mn

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3790414A (en) * 1967-11-15 1974-02-05 Matsushita Electric Ind Co Ltd As-CAST, RARE-EARTH-Co-Cu PERMANENT MAGNET MATERIAL
US3839102A (en) * 1967-11-15 1974-10-01 Matsushita Electric Ind Co Ltd Permanent magnet
US3664892A (en) * 1968-01-31 1972-05-23 Gen Electric Permanent magnet material powders having superior magnetic characteristics
US4378331A (en) * 1969-01-24 1983-03-29 U.S. Philips Corporation Hydrides of the formula AD N HM
DE2003749A1 (en) * 1969-01-24 1970-07-30 Philips Nv Hydrides with the formula ABnHm
US3956031A (en) * 1969-12-24 1976-05-11 Texas Instruments Incorporated Magnetic materials and the formation thereof
US3919004A (en) * 1970-04-30 1975-11-11 Gen Electric Liquid sintered cobalt-rare earth intermetallic product
US3655463A (en) * 1970-04-30 1972-04-11 Gen Electric Sintered cobalt-rare earth intermetallic process using solid sintering additive
US3655464A (en) * 1970-04-30 1972-04-11 Gen Electric Process of preparing a liquid sintered cobalt-rare earth intermetallic product
US3652343A (en) * 1970-09-14 1972-03-28 Gen Electric Permanent magnet material powders having superior magnetic characteristics
US3755007A (en) * 1971-04-01 1973-08-28 Gen Electric Stabilized permanent magnet comprising a sintered and quenched body of compacted cobalt-rare earth particles
US3919003A (en) * 1971-12-17 1975-11-11 Gen Electric Sintered cobalt-rare earth intermetallic product
US3905839A (en) * 1971-12-17 1975-09-16 Gen Electric Liquid sintered cobalt-rare earth intermetallic product
US4003767A (en) * 1971-12-27 1977-01-18 Bbc Brown Boveri & Company Limited Procedure for the production of permanent magnetic sinter bodies using a ternary cobalt-lanthanoid compound
US3844850A (en) * 1972-04-17 1974-10-29 Gen Electric Large grain cobalt-samarium intermetallic permanent magnet material and process
US3919002A (en) * 1972-06-15 1975-11-11 Gen Electric Sintered cobalt-rare earth intermetallic product
US3905840A (en) * 1972-06-15 1975-09-16 Gen Electric Sintered cobalt-rare earth intermetallic product
US3856579A (en) * 1972-12-04 1974-12-24 Battelle Development Corp Sputtered magnetic materials comprising rare-earth metals and method of preparation
US3947295A (en) * 1973-02-09 1976-03-30 Matsushita Electric Industrial Co., Ltd. Hard magnetic material
US3997371A (en) * 1973-11-12 1976-12-14 Hitachi Metals, Ltd. Permanent magnet
US4075042A (en) * 1973-11-16 1978-02-21 Raytheon Company Samarium-cobalt magnet with grain growth inhibited SmCo5 crystals
US4002508A (en) * 1974-08-27 1977-01-11 Aimants Ugimag S.A. Composition for permanent magnets of the family "rare earths-transition metals" and process for producing such a magnet
US4210471A (en) * 1976-02-10 1980-07-01 Tdk Electronics, Co., Ltd. Permanent magnet material and process for producing the same
US4213803A (en) * 1976-08-31 1980-07-22 Tdk Electronics Company Limited R2 Co17 Rare type-earth-cobalt, permanent magnet material and process for producing the same
US4370296A (en) * 1978-03-21 1983-01-25 Fdx Associates, L.P. Toroidal fusion reactor having ohmic heating coil substantially adjacent toroidal fusion region
US4370295A (en) * 1978-03-21 1983-01-25 Fdx Associates, L.P. Fusion-fission power generating device having fissile-fertile material within the region of the toroidal field coils generating means
US4710242A (en) * 1980-08-11 1987-12-01 Fujitsu Limited Material for temperature sensitive elements
US4382061A (en) * 1980-10-25 1983-05-03 Th. Goldschmidt Ag Alloy preparation for permanent magnets
US4536233A (en) * 1980-12-16 1985-08-20 Kabushiki Kaisha Suwa Seikosha Columnar crystal permanent magnet and method of preparation
US5382303A (en) * 1992-04-13 1995-01-17 Sps Technologies, Inc. Permanent magnets and methods for their fabrication
US5781843A (en) * 1992-04-13 1998-07-14 The Arnold Engineering Company Permanent magnets and methods for their fabrication

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BE700002A (en) 1967-12-15
DE1558550B2 (en) 1977-06-30
DE1558550A1 (en) 1970-04-09
NO122852B (en) 1971-08-23
NL6608335A (en) 1967-12-18
SE332866B (en) 1971-02-22
DK117970B (en) 1970-06-22
CH499857A (en) 1970-11-30
AT286657B (en) 1970-12-28
GB1187853A (en) 1970-04-15
ES341762A1 (en) 1968-10-16

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