PROCESS FOR THE PRODUCTION OF ORDERED ARRAYS OF FERROMAGNETICCOMPOSITES

Abstract: The invention relates to a method for the directional solidification of a magnetic composite material consisting of ordered arrays of a ferromagnetic composite selected from REM/M; REM mixtures; REM/REM/M; REU(M)/REU(M); U/M and U/UM systems, wherein RE is a rare earth metal, M is a transition or noble metal and U is uranium, which comprises the directional solidifying of a eutectic, off-eutectic or peritectic composition of a precursor alloy of a system as defined above at a solidifying rate of 0.05 to 100 cm/h and at a thermal gradient of from 10 to 1000°C/cm.

Description: ORDERED ARRAYS OF FERROMAGNETIC COMPOSITES This invention relates to the ordered arrays of ferromagnetic composites. The ability to produce rare earth-transition containing and uranium-transition containing systems which enclose single domains, in an ordered array, to allow the permanent magnetic properties of these materials to approach theoretical maximum limits has not been possible until now. It is an object of this invention to provide a method for the production of ordered arrays of ferromagnetic composites comprising such systems. In practice, these permanent magnet materials offer significant manufacturing as well as application advantages over existing rare earth-cobalt permanent magnets. In accordance with this invention, there is provided a method for the directional solidification of a magnetic composite material consisting of ordered arrays of a ferromagnetic composite selected from REM/M, REM mixtures, REM/RE/M,REU(M)/REU(N),U/M and U/UM systems, wherein RE is a rare earth metal, M is a transition or noble metal and U is uranium, which comprises the directional solidifying of a eutectic, off-eutectic or peritectic composition of a precursor alloy of a system as defined above at a solidifying rate of 0.05 to 100 cm/h and at a thermal gradient of from 10 to 1000 OC/cm. In one embodiment, the above method is employed for the production of ordered arrays of a ferromagnetic composite of a REM/M system such as Sm2Col7/Co and Sm2Fel7/Fe wherein a precursor eutectic REM/N composition is directionally solidified at a solidifying rate of about 20 cm/h and at a thermal gradient of 200 OC/cm. In another embodiment, the above method is employed for the production of ordered arrays of a REM mixture system such as Sm2Col7/SmCo5 and Sm2Fel7/SmFe3 wherein a precursor peritectic REM mixture composition as directionally solidified at a solidifying rate of about 0.5 cm/h and at a thermal gradient of 100 C/cm. In another embodiment, the above method is employed for the production of ordered arrays of a REM/REM/M system such as (MM)2 Co17/(MM)Co5/Co wherein MM is a combination of rare earths La, Ce, Nd, Pr and Sm wherein a precursor REM/REM/M composition is-direction-¯ ally solidified at a solidifying rate of 0.05 to 50 cm/h and at a thermal gradient of from 10 to 1000 C/cm. In other embodiments, the above method is employed for the production of ordered arrays of the systems REU(M)/REU(M), U/M and U/UM. The ferromagnetic composites employed in the herein disclosed method can be categorized as follows: A FOR SYSTEMS REM/M, REM MIXTURES, REM/REM/M AND REU(M)/REU(M): 1 Single domain fibres of (REXSm1-x)2M17 in an M-matrix, with 0ixi 1 and RE = one or more of Ce, Pr Nd 2 single domain fibres of (RExSm1-x)2M17 in a (REySm1-y)M5 matrix, with 0#x#1 and 0#y#1 and RE = one or more of Ce, Pr, Nd. 3 single domain fibres of (RExSml x)M5 in a (REySm1-y)2M17 matrix, with 0#x#1 and 0#Y#1 and RE = one or more of Ce, Pr, Nd 4 fibres of M in a single pinned domain (RExSm1z)?Mi7 matrix 5 single domain fibres of (REXSm1-x)M5 in a pinned single domain (RExSm1-x)2M17 matrix 6 single domain fibres of (RExSm1-x)2M17 in a pinned single domain (RExSm1-x)M5 matrix 7 alternating or concentric arrays of (RExSm1-x)2M17 and (REySm1-y)M5 single domains in a M matrix, with 0 # x # 1 and 0 # y # 1 and RE = one or more of Ce, Pr, Nd 8 alternating or concentric arrays of (RE1-xSmx)2M17 and (REySm1-Y)M5, single domains with 0 # x # 1 and o # y # 1 and RE = one or more of Ce, Pr, Nd 9 single domain fibres of (RExSm1-x)M5 in a (REySm1-y)2M7 matrix, with 0 # x # 1 and 0 # y # 1 and RE = one or more of Ce, Pr, Nd 10 alternating or concentric arrays of (REx Sm1-x)M5 and (REySm1-y) 2M7, single domains, with 0 # x # 1 and o v y # 1 and RE = one or more of Ce, Nd, Pr 11 alternating or concentric arrays of (RExSm1-x)2M17 and (REySm 1-z)M5 single domains in a (REzSm1-z)2M7 matrix, with 0 # x # 1 and 0 # (y) # 1 and O # z # 1 and RE = one or more of Ce, Nd, Pr 12 alternating or concentric arrays of (RExSml-x)2M17 and (REySm1-y)M5 and (REzSm1-z)2M7 single domains, and RE = one or more of Ce, Pr, Nd 13 alternating or concentric arrays of (RExSm 1-z) 2M17 and (REySm1-y)M5 single domains and M with 0 # # x ( 1 and 0 # y # 1 and RE = one or more of Ce, Pr, Nd 14 alternating or concentric arrays of (RExSm1-x)2M17 and M single domains with 0 # x # 1 and RE = one or more of Ce, Pr, Nd 15 single domain fibres of (MM)2M17 in a M-matrix 16 single domains fibres of (MM)2M17 in a (MM)M5 matrix 17 single domain fibres of (MM)M5 in a (MM)2M17 matrix 18 alternating or concentric arrays of (MM)2M17 and (MM)M5 single domains in a M-matrix 19 alternating or concentric arrays of (MM)2M17 and (MM)M5 single domains 20 fibres of M in a pinned single domain (MM)2M17 matrix 21 single domain fibres of (MM)M5 in a pinned single domain (MM)2M17 matrix 22 single domain fibres of (MM)2M17 in a pinned single domain (MM)M5 matrix 23 single domain fibres of (MM)M5 in a (MM)2M7 matrix .24 alternating or concentric arrays of (MM)M5 and (MM)2M7 single domains 25 single domain fibres of (MM)2M7 in a pinned single domain (MM)M matrix 5 26 alternating or concentric arrays of (MM)2M17 and (MM)M5 and (MM)2M7 single domains 27 alternating or concentric arrays of (MM)M5 and (MM)2M7 single domains and M 28 alternating or concentric arrays of (!DI)2M17 single domains and M wherein the above 28 systems: Co refers to the transition metal cobalt Sm refers to the rare earth metal samarium Nd refers to the rare earth metal neodymium Pr refers to the rare earth metal praseodymium Ce refers to the rare earth metal cerium M refers to one or more of the transition or noble metals MM refers to some combination of the rare earth metals lanthanum, cerium, neodymium, praseodymium and samarium. pinned single domain refers to single domain structures whose size is limited by an array of dispersed fibres. The fibres serve to perturb the crystal lattice of the matrix phase so as to prevent domain nucleation or domain wall motion between nearest neighbour domains of the matrix phase. In the single domain structure, the easy axis of magnetization is parallel to the major axis and growth direction. single domain fibre refers to a regularly shaped structure with a large aspect ratio whose easy axis of magnetization is parallel to the major axis and growth direction. B FOR SYSTEMS U/M AND U/UM: 1 single domain fibres of (REXU1-x)2M11 in a M matrix, with 0 < x < 1 2 single domain fibres of (RExU1-x)2M11 in a (REyU1-y)M4 matrix with 0 # x # 1 and 0 # y # 1 3 alternating or concentric arrays of (RExU1-x)2M11 and (REyU1-y)M4 single domains in a M matrix with 0 # x # 1 and O ( y < 1 4 alternating or concentric arrays of (RExU1-x)2M11 and (REyU1-y)M4 and (REzU1-z)M3 single domains in a M matrix with 0 c x # 1, 0 c y # 1 and 0 # z < 1 5 single domain fibres of (REyU1-y)M4 in a pinned single domain (RExU1-x)2M11 matrix with 0 < x < 1 and 0 # y # 1 6 fibres of M in a pinned single domain (RExU1-x)2M11 matrix with 0 # x < 1 7 single domain fibres of (MMxU1-y)2M11 ina M matrix with 0 < x < 1 8 single domain fibres of (MMxU1-x)2M11 in a (MMyU1-y)M4 matrix with 0 < x < 1 and 0 < y < 1 9 alternating or concentric arrays of (MMxU1-x)2M11 and (MMyU1-y)M4 single domains in a M matrix with O # x < 1 and 0 < y # 1 1 10 alternating or concentric arrays of (MMxU1-x)2M11 and (MMyU1-y)M4 and (MMzU1-z)M3 single domains in a M matrix with O 0 < x < 1, 0 < y < 1 and O # z # 1 11 single domain fibres of (MMyU1-y)M4 in a pinned single domain (MMxU1-x)2M11 matrix with 0 # x # 1 and 0 # y # 1 12 fibres of M in a pinned single domain (MMxU1-x)2M11 matrix with-0 < x # 1 wherein the above 12 systems: RE refers to'one or more of the rare earth metals M refers to one or more of the transition or noble metals MM refers to some combination of the rare earth metals lanthanum, cerium, neodymium, praseodymium and samarium U refers to the actinide uranium pinned single domain refers to single domain structures whose size is limited by an array of dispersed fibres. The fibres serve to perturb the crystal lattice of the matrix phase so as to prevent domain nucleation or domain wall motion between nearest neighbour domains of the matrix phase. In the single domain structure, the easy axis of magnetization is parallel to the major axis and growth direction. single domain fibre refers to a regularly shaped structure with a large aspect ratio whose easy axis of magnetiyation is parallel to the major axis and growth direction. The method employed herein for the production of ordered arrays of ferromagnetic composites selected from the systems just described involves the directional solidification of a eutectic, off-eutectic or peritectic composition of a precursor alloy of the aforedescribed systems at a solidifying rate of 0.05 to 100 cm/h at a thermal gradient of from 10 to 1000 C/cm. More particularly, the directional solidification of eutectic, off-eutectic and peritectic compositions involves the steps of: 1 Preparation of starting solidification charges using high purity (99,999) rare earth, transition metal and/ or uranium which-are melted together in an evacuated, pyrolyzed boron llitride crucible above about 13000C, i.e. the temperatlire at which the specific REM/M, REM mixture, REM/REM/M, REU( > I)/REU(M), U/M and U/UM compound forms. The melt is electromagnetically stirred using RF induction heating until a uniform starting composition is achieved. 2 Portions of these starting charges are then remelted in a specially designed pyrolyzed boron nitride/ aluminum oxide inner/outer, evacuated sample crucible and directionally solidified in a three zone Bridgman Stockbarger apparatus. The three zones are individually controlled so as to maintain the desired thermal gradient and yet achieve unidirectional heat flow (directional solidification) at the advancing liquid solid interface. Solidification is performed in either sealed or active vacuum pumping conditions. 3 Controlled directional solidification produces an aligned array of single domain-type ferromagnetic species, whose cross-sectional morphology is dependent on the specilf elloy system and solidification processing conditions. Reference is now made to the accompanying drawings, in which: Figure la is a representation of a eutectic phase diagram; Figures lb, Ic, and ld depict the plane fronts for various directional solidifications of magnetic composite materials; Figure le depicts a plane front solidification with radial extraction of beat resulting in domain structures parallel to the radial growth direction; Figures 2a, 2b, and 2c depict coupled, aligned composite arrays of solidified alloys; and Figure 2A Depicts a solidified alloy in an aligned composite array of more than two phases. As is seen in Figure la (which represents a typical eutectic phase diagram), it is possible to undercool the melt by an amount2ST in eutectic, off-eutectic and peritectic directional solidification to achieve coupled, aligned composite arrays (see figures 2a, 2b and 2c), at some intermediate alloy composition of Co where Co lies between the maximum composition of the terminal solid solution Css and the composition of the eutectic compound CE. It is also possible to solidify these alloys in aligned composite arrays of more than two (2) phases (in alternating or concentric arrays, see figure 2d) since ternary or more complex alloy systems solidify via a eutectic reaction. This undercooling can be accomplished by an appropriate choice of the ratio G/V (where G is the thermal gradient at the solidification interface and V is the rate at which the plane front solidification interface moves). Since the diameter of the eutectic compound fibres, d, and the inter-fibre spacing, 7k, is also a function of G and V and the composition Co, d = f(G, V, Co) # = g(G, V, Co) It is possible to establish an ordered array of fibres of ss (and/or ss1, ss2) in a matrix such that d lies within the dimensions necessary for magnetic single domains and Xis small enough to ensure a large volume fraction of the permanent magnet phase (see figure Ib) and/or the matrix will consist of magnetic as well as either pinned (as in figure 2c) or isolated and enclosed single domains (as in figure 2b). The specific manufacturing and application advantages of systems described above in Category A over existing rare earth-cobalt magnets are: 1 Eliminate grinding, pressing and sintering operations. 2 Eliminate non-uniformity of particle shape. 3 Eliminate necessity to align particles in an external magnetic field. 4 Eliminate strain induced by grinding particles. 5 Eliminate necessity to anneal final product to reduce strain. 6 Eliminate oxidation of final product due to anneal. 7 Significantly reduce adverse oxidation of rare earth cobalt composite particles by growing them (and thus permanently enclosing them) in a protective matrix. 8 Significantly improve ductility and machinability of final product material. 9 Increase significantly number of medical and biological applications of rare earth-cobalt magnets since oxidation and subsequent decomposition will be greatly reduced. 10 Increase significantly dynamic applications since recoil energy will be nearly maximised and lack of oxidation and subsequent decomposition will allow use of these magnetic composites at elevated temperatures g 1500C). Improvement of these systems over the best existing permanent magnets include: 1 Up to a 40% increase in saturation magnetization, Ms, 2 Up to a 70% increase in remanent induction, Br. 3 Up to a 170% increase in static energy product, (BH)max 4 Up to a 300% increase in dynamic energy product or useful recoil energy, (BH)u' 5 Significant increase in the intrinsic coercivity, Hci or MHC approaching the anisotropy field HA. This represents an increase up to 300% over the best current intrinsic coercivities. 6 The ability to "tune" or adjust the various figures of merit to achieve a maximised set of characteristics for differing applications by changing the chemistry and/or morphology of these magnetic composites. The specific manufacturing and application advantages of systems described above in Category B over existing rare earth-cobalt magnets are: 1 Eliminate grinding, pressing and wintering operations 2 Eliminate non-uniformity of particle shapes. 3 Eliminate necessity to align particles in an external magnetic field. 4 Eliminate strain induced by grinding particles. 5 Eliminate necessity to anneal final product to reduce strain. 6 Eliminate oxidation of final product due to anneal. 7 Significantly reduce adverse oxidation of rare earth cobalt composite particles by growing them (and thus permanently enclosing them) in a protective matrix. 8 Significantly improve ductility and machinability of final product material. 9 Increase significantly number of medical and biological applications of rare earth-cobalt magnets since oxidation and subsequent decomposition will be greatly reduced. 10 Increase significantly dynamic applications since recoil energy will be nearly maximised and lack of oxidation and subsequent decomposition will allow use of these magnetic composites at eleve.ted temperatures (21500c). 11 Since'U availability in stable (radioactive-cool) UF4 and UF6 exceeds the present world inventory of rare earth by a factor of x 1000 the anticipated shortage of rare earth in future magnet applications will be eliminated. 12 Significant cost savings per pound over rare earth cobalt magnets through use of uranium and transition and noble metal additions other than cobalt. Improvement of these systems over the best existing permanent magnets include: 1 Ability to equal present or future anticipated permanent magnet figures of merit such as remanent induction (nr) or static andsdynamic energy product (BH)static and (B)dynamic through alloying with rare earth or misch-metal additions. The ability to grow aligned U/M, u/im and REU/REU compounds in an ordered array enables: 1 The growth of single domain particles for the first time. 2 The shape of the single domains to be very long fibres which nearly maximise the shape anisotropy for particles in the shape of a prolate spheroid (see figs. 2a, 2b, 2c, and 2d). 3 The near alignment of all single domain structures along the growth direction (which corresponds to the easy-axis of magnetization) thus nearly maximising the effect of the very large magnetocrystalline anisotropies of these compounds.

Claims: CLAIMS 1 A method for the directional solidification of a magnetic composite material consisting of ordered arrays of a ferromagnetic composite selected from REM/N; REM mixtures; REM/REM/M; REU(M)/REU(M); U/M and U/UN systems, wherein RE is a rare earth metal, M is a transition or noble metal and U is uranium, which comprises the directional solidifying of a eutectic, off-eutectic or peritectic composition of a precursor alloy of a system as defined above at a solidifying rate of 0.05 to 100 cm/h and at a thermal gradient of from 10 to 10000C/cm. 2 The method of claim 1 for the production ordered arrays of a ferromagnetic composite of a REM/N system, wherein a precursor eutectic REM/N composition is directionally solidified at a solidifying rate of about 20 cm/h and at a thermal gradient of 2000C/cm. 3 The method of claim 2 for the production of Sm2Col7/Co (5:1 by weight). 4 The method of claim 2 for the production of Sm2Fel7/Fe (5:1 by weight). 5 The method of claim 1 for the production of ordered arrays of a ferromagnetic composite of a REM mixture system, wherein a precursor peritectic REM mixture composition is directionally solidified at a solidifying irate of about 0.5 cm/h and at a thermal gradient of 1000C/cm. 6 The method of claim 5 for the production of Sm2Col7/ SmCo5 (1:3 by weight). 7 The method of claim 5 for the production of Sm2Fel7/ SmFe3 (5:1 by weight). 8 The method of claim 1 for the production of ordered arrays of a ferromagnetic composite of a REM/REM/M system wherein a precursor REM/REM/M composition is directionally solidified at a solidifying rate of 0.05 to 50 cm/h and at a thermal gradient of from 10 to 10000C/cm. 9 The method of claim 8 for the production of (MM)2CO17/ (MM)Co5/Co wherein MM is a combination of rare earths La, Ce, Nd, Pr and Sm. 10 The method of claim 1 for the production of ordered arrays of a ferromagnetic composite of a REU(M)/REU(M) system, wherein a precursor REU(M)/REU(M) composition is directionally solidified at a solidifying rate of 0.05 to 50 cm/h and at a thermal gradient of from 10 to 1000C/cm. 11 The method of claim 1 for the production of ordered arrays of a ferromagnetic composite of a U/M system, wherein a precursor U/M composition is directionally solidified at a solidifying rate of 0.05 to 50 cm/h and at a thermal gradient of from 10 to 10000C/cm. 12 The method of claim 1 for the production of ordered arrays of a ferromagnetic composite of a U/UM system, wherein a precursor U/UM composition is directionally solidified at a solidifying rate of 0.05 to 50 cm/h and at a thermal gradient of from 10 to 100000/cm. 13 The product obtained by the method of claim 1.

Inventors: LARSON, DAVID J., PIRICH, RONALD G.
Applicants: GRUMMAN AEROSPACE CORPORATION
Application year: 1984
Main classification: H01F1
IPC codes: C30B21, C22C1, H01F1, C22C19, C22C38, C22C43, C30B29