Noise filter comprising a soft magnetic alloy ribbon core

Description

BACKGROUND OF THE INVENTION
The present invention relates to a noise filter incorporated in, for example, a switching power source or a DC-DC converter.
In recent years, a reduction in the size, weight and production cost of the office automation (OA) equipment has advanced, and the significance of the above-described types of power sources in the OA equipment has grown, thus increasing a demand for a reduction in the size of such a power source or a noise filter incorporated in the power source.
Noise filters, whose size reduction has been demanded, must have a higher attenuation capability in order to cope with higher frequencies.
Generally, the characteristics required for the soft magnetic material for use in a magnetic core of a noise filter are as follows:
(1) High saturation magnetization
(2) High magnetic permeability
(3) Low coercive force, and
(4) Thin shape which can easily be formed.
In view of the above, various alloys have been studied in the course of developing such soft magnetic alloys for use as in a magnetic core of a noise filter. Particularly, alloys exhibiting higher saturation magnetization and higher permeability have been studied in order to achieve reduction in the size of the noise filter and an increase in the frequencies that the noise filter can cope with.
Conventional materials for use in the magnetic core of a noise filter are crystalline alloys, such as Fe--Al--Si alloy Permalloy or silicon steel, and Fe-based or Co-based amorphous alloys.
However, Fe--Al--Si alloy suffers from a disadvantage in that the saturation magnetization thereof is as low as about 11 kG, although it exhibits excellent soft magnetic characteristics. Permalloy, which has an alloy composition exhibiting excellent soft magnetic characteristics, also has a saturation magnetization as low as about 8 kG. Silicon steel (Fe--Si alloys) has inferior soft magnetic characteristics, although they have a high saturation magnetization.
Co-based amorphous alloys have an insufficient saturation magnetization, which is about 10 kG, although they exhibit excellent soft magnetic characteristics. Fe-based amorphous alloys tend to exhibit insufficient soft magnetic characteristics, although they have a high saturation magnetization, which is 15 kG or above. Further, amorphous alloys are insufficient in terms of the heat stability and this deficiency may cause a problem.
Thus, it is conventionally difficult to provide a material exhibiting both high saturation magnetization and excellent soft magnetic characteristics. This in turn makes it difficult to provide a noise filter exhibiting sufficient attenuation characteristics.
SUMMARY OF THE INVENTION
The present invention provides a noise filter which comprises: an annular magnetic core made of a soft magnetic alloy ribbon mainly made of Fe and containing B and at least one element selected from a group consisting of Ti, Zr, Hf, Nb, Ta, Mo and W, at least 50% of the soft magnetic alloy structure being composed of body-centered cubic structured fine grains having an average grain size of 30 nm or below; a casing accommodating the magnetic core; a pair of coils separated from each other; and an electrical circuit for connecting a core element made up of the magnetic core, the casing and the coils.
In the present invention, various modifications and changes in the composition of the soft magnetic core ribbon may be made. Composition examples of the soft magnetic alloy ribbon will be described below. Composition 1: Fe.sub.b B.sub.x M.sub.y
where M is at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W combined with Zr and/or Hf, 75<b<93 atomic percent, 0.5<x<10 atomic percent, and 4<y<9 atomic percent. Composition 2: Fe.sub.b B.sub.x M.sub.y X.sub.u
where M is at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W combined with Zr and/or Hf, X is at least one element selected from a group consisting of Cr, Ru, Rh and Ir, 75<b<93 atomic percent, 0.5<x<10 atomic percent, 4<y<9 atomic percent, and u<5 atomic percents. Composition 3: (Fe.sub.1-a Z.sub.a).sub.b B.sub.x M.sub.y
where Z is Co and/or Ni, M is at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W combined with Zr and/or Hf, a<0.1 atomic percents, 75<b<93 atomic percent, 0.5<x<10 atomic percent, and 4<y<9 atomic percent. Composition 4: (Fe.sub.1-a Z.sub.a).sub.b B.sub.x M.sub.y X.sub.u
where Z is Co and/or Ni, M is at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W combined with Zr and/or Hf, X is at least one element selected from a group consisting of Cr, Ru, Rh and Ir, a <0.1 atomic percent, 75<b<93 atomic percent, 0.5<x<10 atomic percent, 4<y<9 atomic percent, and u<5 atomic percent. Composition 5: Fe.sub.b B.sub.x M'.sub.y
where M' is at least one element selected from a group consisting of Ti, V, Nb, Ta, Mo and W combined with Nb, 75<b<93 atomic percent, 6.5<x<10 atomic percent, and 4<y<9 atomic percent. Composition 6: Fe.sub.b B.sub.x M'.sub.y X.sub.u
where M' is at least one element selected from a group consisting of Ti, V, Nb, Ta, Mo and W combined with Nb, X is at least one element selected from a group consisting of Cr, Ru, Rh and Ir, 75<b<93 atomic percent, 6.5<x<10 atomic percent, 4<y<9 atomic percent, and u<5 atomic percents. Composition 7: (Fe.sub.1-a Z.sub.a).sub.b B.sub.x M'.sub.y
where Z is Co and/or Ni, M' is at least one element selected from a group consisting of Ti, V, Nb, Ta, Mo and W combined with Nb, a<0.1 atomic percent, 75<b<93 atomic percent, 6.5<x<10 atomic percent, and 4<y<9 atomic percent. Composition 8: (Fe.sub.1-a Z.sub.a).sub.b B.sub.x M'.sub.y X.sub.u
where Z is Co and/or Ni, M' is at least one element selected from a group consisting of Ti, V, Nb, Ta, Mo and W combined with Nb, X is at least one element selected from a group consisting of Cr, Ru, Rh and It, a<0.1 atomic percent, 75<b<93 atomic percent, 6.5<x<10 atomic percents, 4<y<9 atomic percents, and u<-5 atomic percents. Composition 9: Fe.sub.b B.sub.x M.sub.y T.sub.z
where M is at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W combined with Zr and/or Hf, T is at least one element selected from a group consisting of Cu, Ag, Au, Pd, Pt and Bi, 75<b<93 atomic percents, 0.5<x<18 atomic percent, 4<y<10 atomic percents, and z<4.5 atomic percent. Composition 10: Fe.sub.b B.sub.x M.sub.y T.sub.z X.sub.u
where M is at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W combined with Zr and/or Hf, T is at least one element selected from a group consisting of Cu, Ag, Au, Pd, Pt and Bi, X is at least one element selected from a group consisting of Cr, Ru, Rh and Ir, 75<b<93 atomic percent, 0.5<x<18 atomic percents, 4<y<10 atomic percent, z<4.5 atomic percent, and u<5 atomic percents. Composition 11: (Fe.sub.1-a Z.sub.a).sub.b B.sub.x M.sub.y T.sub.z
where Z is Co and/or Ni, M is at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W combined with Zr and/or Hf, T is at least one element selected from a group consisting of Cu, Ag, Au, Pd, Pt and Bi, a<0.1 atomic percent, 75<b<93 atomic percent, 0.5<x<18 atomic percent, 4<y<10 atomic percent, and z<4.5 atomic percent. Composition 12: (Fe.sub.1-a Z.sub.a).sub.b B.sub.x M.sub.y T.sub.z X.sub.u
where Z is Co and/or Ni, M is at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W combined with Zr and/or Hf, T is at least one element selected from a group consisting of Cu, Ag, Au, Pd, Pt and Bi, X is at least one element selected from a group consisting of Cr, Ru, Rh and It, a <0.1 atomic percent, b<75 to 93 atomic percent, 0.5<x<18 atomic percent, 4<y<10 atomic percent, z<4.5 atomic percent, and u<5 atomic percent, and Composition 13: Fe.sub.b B.sub.x M'.sub.y T.sub.z
where M' is at least one element selected from a group consisting of Ti, V, Nb, Ta, Mo and W and combined with any of Ti, Nb and Ta, T is at least one element selected from a group consisting of Cu, Ag, Au, Pd, Pt and Bi, 75<b<93 atomic percent, 6.5<x<18 atomic percent, 4<y<10 atomic percent, and z<4.5 atomic percent. Composition 14: Fe.sub.b B.sub.x M'.sub.y T.sub.z X.sub.u
where M' is at least one element selected from a group consisting of Ti, V, Nb, Ta, Mo and W combined with any of Ti, Nb and Ta, T is at least one element selected from a group consisting of Cu, Ag, Au, Pd, Pt and Bi, X is at least one element selected from a group consisting of Cr, Ru, Rh and Ir, 75<b<93 atomic percent, 6.5<x<18 atomic percent, 4<y<10 atomic percent, z<4.5 atomic percent, and u<5 atomic percent. Composition 15: (Fe.sub.1-a Z.sub.a).sub.b B.sub.x M'.sub.y T.sub.z
where Z is Co and/or Ni, M' is at least one element selected from a group consisting of Ti, V, Nb, Ta, Mo and W combined with any of Ti, Nb and Ta, T is at least one element selected from a group consisting of Cu, Ag, Au, Pd, Pt and Bi, a<0.1 atomic percent, 75<b<93 atomic percent, 6.5<x<18 atomic percent, 4<y<10 atomic percent, and z<4.5 atomic percent. Composition 16: (Fe.sub.1-a Z.sub.a).sub.b B.sub.x M'.sub.y T.sub.z X.sub.u
where Z is Co and/or Ni, M' is at least one element selected from a group consisting of Ti, V, Nb, Ta, Mo and W combined with any of Ti, Nb and Ta, T is at least one element selected from a group consisting of Cu, Ag, Au, Pd, Pt and Bi, X is at least one element selected from a group consisting of Cr, Ru, Rh and Ir, a<0.1 atomic percent, 75<b<93 atomic percent, 6.5<x<18 atomic percent, 4<y<10 atomic percent, z<4.5 atomic percent, and u<5 atomic percent.
In each of the above compositions preferably 0.2<z<4.5 atomic percent.

BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 (a) is a perspective view of a core element of a noise filter according to the present invention;
FIG. 1 (b) is a section taken along the line b--b of FIG. 1 (a);
FIG. 1 (c) is a perspective view of a magnetic core of the noise filter of FIG. 1 (a);
FIG. 2 is a graphic representation showing the relationship between the heating rate and the permeability of alloys according to the present invention;
FIG. 3 (a) is a graphic representation showing the relationship between the saturation magnetization and the annealing temperature of an alloy according to the present invention;
FIG. 3 (b) is a graphic representation showing the relationship between the effective permeability and the annealing temperature of an alloy according to the present invention;
FIG. 4 is an X-ray diffraction pattern showing changes in the structure of an alloy according to the present invention caused by the heat treatment;
FIG. 5 is a schematic view of a microscopic photograph showing the structure of a heat treated alloy according to the present invention;
FIG. 6 shows permeability when the proportion of Zr, that of B and that of Fe in an alloy heat treated at 600.degree. C. according to the present invention are changed;
FIG. 7 shows permeability when the proportion of Zr, that of B and that of Fe in an alloy heat treated at 650.degree. C. according to the present invention are changed;
FIG. 8 shows saturation magnetization when the proportion of Zr, that of B and that of Fe in an alloy according to the present invention are changed;
FIG. 9 shows saturation magnetization when the proportion of Zr, that of B and that of Fe in an alloy according to the present invention are changed;
FIG. 10 is a graphic representation showing the relationship between the proportion of Co or Ni in an alloy according to the present invention and the permeability thereof;
FIG. 11 shows the relationship between the effective permeability and the annealing temperature in an alloy according to the present invention;
FIG. 12 is an X-ray diffraction pattern showing changes in the structure of an alloy according to the present invention caused by the heat treatment;
FIG. 13 is a schematic view of a microscopic photograph showing the structure of a heat treated alloy according to the present invention;
FIG. 14 shows the magnetic characteristics when the proportion of Fe+Cu, that of B and that of Zr are changed in an alloy according to the present invention;
FIG. 15 is a graphic representation showing the relationship between changes in the proportion of Hf in an alloy according to the present invention and the permeability thereof;
FIG. 16 shows the magnetic characteristics when the proportion of B, that of Zr+Nb and that of Fe+Cu in an alloy according to the present invention are changed;
FIG. 17 is a graphic representation showing the relationship between the proportion of Cu and the effective permeability in an alloy according to the present invention;
FIG. 18 is a graphic representation showing the relationship between the proportion of Co and the permeability in an alloy according to the present invention;
FIG. 19 is a graphic representation showing the relationship between the effective permeability and the annealing temperature in an alloy according to the present invention;
FIG. 20 is a graphic representation showing the relationship between the proportion of B and the effective permeability in an alloy according to the present invention;
FIG. 21 is a graphic representation showing the relationship between the proportion of Nb and the effective permeability in an alloy according to the present invention;
FIG. 22 is an X-ray diffraction pattern showing changes in the structure of an alloy according to the present invention caused by the heat treatment;
FIG. 23 is a schematic view of a microscopic photograph showing the structure of a heat treated alloy according to the present invention;
FIG. 24 shows permeability when the proportion of Fe+Cu, that of B and that of Nb are changed in an alloy according to the present invention;
FIG. 25 shows saturation magnetization when the proportion of Fe+Cu, that of B and that of Nb are changed in an alloy according to the present invention;
FIG. 26 is a graphic representation showing the relationship between the proportion of Cu and the effective permeability in an alloy according to the present invention;
FIG. 27 is a graphic representation showing the relationship between the proportion of Nb, that of Ta and that of Ti and the permeability in an alloy according to the present invention;
FIG. 28 (a) is a graphic representation showing the relationship between the saturation magnetization and the annealing temperature in an alloy according to the present invention;
FIG. 28 (b) is a graphic representation showing the relationship between the effective permeability and the annealing temperature in an alloy according to the present invention;
FIG. 29 is a graphic representation showing the relationship between the proportion of B and the effective permeability in an alloy according to the present invention;
FIG. 30 is an X-ray diffraction pattern showing changes in the structure of an alloy according to the present invention caused by the heat treatment;
FIG. 31 is a schematic view of a microscopic photograph showing the structure of a heat treated alloy according to the present invention;
FIG. 32 shows saturation magnetization when the proportion of Fe, that of B and that of Nb are changed in an alloy according to the present invention;
FIG. 33 is a graphic representation showing the relationship between the proportion of Co or Ni and the permeability in an alloy according to the present invention;
FIG. 34 (a) is a graphic representation showing the relationship between the proportion of Co and the saturation magnetization in an alloy according to the present invention;
FIG. 34 (b) is a graphic representation showing the relationship between the proportion of Co and the magnetostriction in an alloy according to the present invention;
FIG. 34 (c) is a graphic representation showing the relationship between the proportion of Co and the permeability in an alloy according to the present invention;
FIG. 35 shows the relationship between the core loss and the heat treating temperature in an alloy according to the present invention;
FIG. 36 shows the relationship between the heating rate and the permeability in examples of the alloy according to the present invention;
FIG. 37 shows the relationship between the heating rate and the permeability in another examples of the alloy according to the present invention;
FIG. 38 shows the relationship between the heating rate and the permeability in still another examples of the alloy according to the present invention;
FIG. 39 shows the relationship between the heating rate and the permeability in still another examples of the alloy according to the present invention;
FIG. 40 shows the relationship between the average grain size and the coercive force in an alloy according to the present invention;
FIG. 41 shows the crystallization fraction in an alloy according to the present invention;
FIG. 42 shows a JMA plot of the alloy shown in FIG. 41;
FIG. 43 shows a distribution of grain size in an alloy according to the present invention;
FIG. 44 shows a distribution of grain size in an alloy of Comparative Example;
FIG. 45 is a schematic view of a photograph showing the results of the test conducted to specify the grain size in a microscopic photograph which shows the grains of the alloy heat treated at a heating rate of 200.degree. C./min according to the present invention;
FIG. 46 is a schematic view of a photograph showing the results of the test conducted to specify the grain size in a microscopic photograph which shows the grains of the alloy heat treated at a heating rate of 2.5.degree. C./min according to the present invention;
FIG. 47 is a circuit diagram of a noise filter;
FIG. 48 is a circuit diagram showing a method of measuring the pulse damping characteristics;
FIG. 49 is a graphic representation showing the results of the pulse attenuation characteristic test;
FIG. 50 is a circuit diagram showing a method of measuring the damping characteristics in the normal mode;
FIG. 51 is a circuit diagram showing a method of measuring the damping characteristics in the common mode;
FIG. 52 is a graphic representation showing the results of the attenuation characteristic test.

DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described below in more detail.
Since the noise filter according to the present invention employs, as a magnetic core, a special soft magnetic alloy exhibiting high saturation magnetization and high permeability, it exhibits excellent attenuation characteristics and can thus cope with high frequencies.
A manufacturing method of the soft magnetic alloy used in the noise filter according to the present invention can be obtained by a process in which an amorphous alloy having the foregoing composition or a crystalline alloy including an amorphous phase is rapidly cooled (quenched) from a melted state. The manufacturing process includes performing a vapor quenching method such as sputtering or deposition on the quenched alloy, and heat treating the alloy subjected to quenching and vapor quenching processes to precipitate fine grains.
It is possible according to the above-described quenching method to readily manufacture a ribbon-shaped magnetic substance. The annular magnetic core of the noise filter can be formed by coiling the ribbon in a toroidal fashion.
The soft magnetic alloy constituting the magnetic core of the noise filter according to the present invention contains boron (B). B enhances the amorphous phase forming ability of a soft magnetic alloy, improves thermal stability of Fe-base microcrystalline (fine crystalline) structure consisting of Fe and M (.dbd.Zr, Hf, Nb and so on) serves as a barrier for the grain growth, and leaves thermally stable amorphous phase in the grain boundary.
Consequently, in the heat treatment conducted at a wide temperature range of 400.degree. to 750.degree. C., it is possible to obtain a structure mainly composed of body-centered cubic phase (bcc phase) fine grains which have a grain size of 30 nm or below and which do not adversely affect the magnetic characteristics.
Like B, Al, Si, C and P are also elements normally used as amorphous phase forming elements. The soft magnetic alloy according to the present invention may contain these elements.
In order to readily obtain an amorphous phase in the soft magnetic alloy having any of composition Nos. 1 through 4 and 9 through 12, either Zr or Hf, exhibiting excellent amorphous phase forming ability, is added.
Part of the Zr or Hf can be replaced by Ti, V, Nb, Ta, Mo or W from the 4A through 6A group elements of the periodic table. In that case, sufficient amorphous phase forming ability can be obtained by making the proportion of B between 0.5 and 10 atomic percentage. In a case where T (Cu, Ag, Au, Pd, Pt or Bi) is added, the proportion of B is made 0.5 to 18 atomic percent. Further, the addition of Zr or Hf in a solid solution, which does not form a solid solution with Fe, reduces magnetostriction. That is, the amount of Zr or Hf added in a solid solution can be adjusted by changing the heat treatment conditions, whereby magnetostriction can be adjusted to a small value.
Thus, the requirements for low magnetostriction are that fine grains can be obtained under wide heat treatment conditions. Because the addition of B enables fine grains to be manufactured under wide heat treatment conditions, it assures an alloy having low magnetostriction and small crystal magnetic anisotropy and hence excellent magnetic characteristics.
Furthermore, the addition of Cr, Ru, Rh, Ir or V (element X) to the above-described composition improves corrosion resistance. The proportion of any of these elements must be 5 atomic percent or below in order to maintain saturation magnetization to 10 kG or above.
That fine grains can be obtained by partially crystallizing Fe--M (M.dbd.Zr, Hf) type amorphous alloy by a special method has been described from page 217 to page 221 in "CONFERENCE ON METALLIC SCIENCE AND TECHNOLOGY BUDAPEST". The present inventors discovered through researches that the same effect can be obtained with the above-described compositions. This invention is based on that knowledge.
The present inventors consider that the reason why fine grains can be obtained is that the constitutional fluctuation which has already occurred in quenching, which is the amorphous phase forming stage in the manufacture of the alloy, becomes the sites for non-uniform nucleation, thus generating uniform and fine nuclei.
In the soft magnetic alloy employed in the magnetic core of the noise filter according to the present invention, the proportion (b) of Fe or Fe, Co and Ni is 93 atomic percent or below, because the presence of more than 93 atomic percent makes it impossible to obtain a high permeability. The addition of 75 atomic percent or above is more preferable in terms of the saturation magnetization of 10 kG or above.
In the soft magnetic alloy having any of composition Nos. 9 through 16, the inclusion of 4.5 atomic percentage or below of at least one element (element T) selected from a group consisting of Cu, Ag, Au, Pd, Pt and Bi is preferable. Although the presence of 0.2 atomic percents or below of any of these elements makes it difficult to obtain excellent soft magnetic characteristics by the heat treatment process, since permeability is improved and saturation magnetization is slightly improved by increasing the heating rate, the proportion of any of these elements can be 4.5 atomic percent or below, as shown in composition example Nos. 9 through 16. However, when the proportion of any of these elements is between 0.2 and 4.5 atomic percent, excellent soft magnetic characteristics can be obtained without greatly increasing the heating rate. Thus, the more preferred proportion is between 0.2 and 4.5 atomic percent.
Among the above-mentioned elements, the addition of Cu is particularly effective. Although the mechanism in which the addition of Cu, Pd or the like greatly improves soft magnetic characteristics is not known, the present inventors measured the crystallization temperature by the differential thermal analysis, and found that the crystallization temperature of the alloy to which Cu, Pd or the like is added is slightly lower than that of the alloy to which no such an element is added. The present inventors consider that this occurred because the addition of the element accelerated the constitutional fluctuation in the amorphous phase, reducing the stability of the amorphous phase and making crystal phase readily precipitated.
Further, when the non-uniform amorphous phase is crystallized, it is partially crystallized and thus non-uniformly nucleated. Accordingly, fine grains ensuring excellent magnetic characteristics can be obtained.
Further, grain refinement is accelerated by increasing the heating rate. Thus, when the heating rate is great, the proportion of Cu, Pd or the like can be made less than 0.2 atomic percent.
Cu, which does not readily form a solid solution with Fe, has a tendency for phase separation. Accordingly, microstructure fluctuation occurs by heating, and non-uniform amorphous phase, contributing to grain refinement, is readily generated.
Therefore, any element of the same group as Cu, Pd and Pt can be used as long as it lowers the crystallization temperature. Also, other elements, such as Bi, whose solution in Fe is limited, can have the same effect as the above-described one.
In the soft magnetic alloy shown by composition Nos. 5 through 8 and 13 through 17, the addition of Nb and B having amorphous phase forming ability is mandatory in order to facilitate formation of amorphous phase.
Ti, V, Ta, Mo and W which have the same effect as that of Nb, Nb, V and Mo relatively restrict generation of oxide, and thus improve manufacturing yield. Therefore, the addition of these elements eases the manufacturing conditions and ensures inexpensive manufacture, which in turn ensures a reduction in the cost. In a practical operation, an alloy can be manufactured in air or an atmosphere having a gas pressure while an inert gas is partially supplied to a distal end portion of a nozzle.
However, any of these elements is inferior to Zr or Hf in terms of the amorphous phase forming ability. Therefore, the proportion of B is increased in the soft magnetic alloy having any of composition example Nos. 5 through 8 and 13 through 16, and the lower limit of B is set to 6.5 atomic percent.
Where T is added, as in the cases of composition Nos. 13 through 16, the upper limit of B is increased to 18 atomic percent. However, where no T is added, as in the cases of composition Nos. 5 through 8, since the addition of 10 atomic percentage or above of B deteriorates the magnetic characteristics, the upper limit thereof is set to 10 atomic percent.
The reasons for limiting the component elements contained in the soft magnetic alloy employed in the present invention have been described. In addition to the above-mentioned elements, Cr, platinum group elements, such as Ru, Rh or Ir, may also be added in order to improve corrosion resistance. Further, magnetostriction can be adjusted, when necessary, by adding any of elements including Y, rare earth elements, Zn, Cd, Ga, In, Ge, Sn, Pb, As, Sb, Se, Te, Li, Be, Mg, Ca, Sr and Ba.
The composition of the soft magnetic alloy employed in the noise filter according to the present invention remains the same if unavoidable impurities such as H, N, O or S are present in the alloy in an amount which does not deteriorate desired characteristics thereof.
To manufacture the soft magnetic alloy employed in the present invention, it is desirable to perform a heat treatment in which the ribbon obtained by quenching is heated at a predetermined temperature increasing rate, is maintained in a predetermined temperature range and then cooled. A desirable heat treatment temperature is between 400.degree. and 750.degree. C. A desirable heating rate in the heat treatment is 1.0.degree. C./min or above.
The present inventors found that the heating rate during heat treatment affects the permeability of the soft magnetic alloy subjected to the heat treatment. When the heating rate is 1.0.degree. C./min or above, it is possible to manufacture a soft magnetic alloy exhibiting high permeability.
The heating rate is a value obtained by differentiating the temperature of an alloy in a heating furnace with respect to the time.
Examples of the present invention will now be described.
In the following examples, a magnetic core 10 of a noise filter has an annular shape formed by winding an alloy ribbon 12 in a toroidal fashion, as shown in FIG. 1 (c). The magnetic core 10 is accommodated in a casing 14 made of an insulating material, as shown in FIG. 1 (b). Coils 16 and 17 are wound around the casing 14 in the manner shown in FIG. 1 (a) in a state wherein they are separated from each other by an insulating plate 18, whereby a core element 19 is formed.
A resin such as a silicon type adhesive fills a space 24 in the casing 14 to fix the magnetic core 10.
Any insulating material, such as a polyester resin with a filler filled therein, is used to form the casing 14. The provision of the casing 14 may not be necessary in terms of the formation of the core element 19. However, when the magnetic core 10 is accommodated in the rigid casing 14, it is possible to prevent application of a stress caused by the coil 16 to the magnetic core 10 and a resultant damage thereto.
The core element 19 is disposed in an electrical circuit 20 such as that shown in FIG. 47 to constitute a noise filter 22.
According to the present invention, the magnetic material is the alloy ribbon constituting the magnetic core.
The alloy ribbon is manufactured by the single roller melt spinning method. That is, the ribbon is manufactured by ejecting molten metal from a nozzle placed above a single rotating steel roller onto the roller under the pressure of an argon gas, for quenching.
Several types of soft magnetic alloys that can be employed in the noise filter and the characteristics thereof will be described below. Each of the alloy ribbons manufactured in the above method has a width of about 15 mm and a thickness of 15 to 40 .mu.m. However, the width of the ribbon can be changed between 4.5 and 30 mm, while the thickness can be altered between several .mu.m and 50 .mu.m.
Permeability was measured in Examples 1 through 6 by the inductance method on a coiled ribbon ring having an outer diameter of 10 mm and an inner diameter of 6 mm. In Examples 7 through 17, a ribbon formed into a ring-like shape having an outer diameter of 10 mm and an inner diameter of 5 mm was used for measuring permeability.
EXAMPLE 1
We examined the relationship between the heating rate in the heat treatment and the permeability of the soft magnetic alloy subjected to that heat treatment. In this test, heat treatment was conducted on the alloys respectively having the compositions shown in Table 1 at different heating rates (.degree.C./min) and the permeability (.mu.) of the heat treated alloys was measured. Heat treatment was performed using an infrared image furnace which held the alloy in a vacuum at 650.degree. C. The cooling rate after the heat treatment was fixed to 10.degree. C./min. Permeability was measured under the conditions of 1 kHz and 0.4 A/m (5 mOe) using an impedance analyzer. The results of the measurements are shown in Table 1 and FIG. 2.
In order to further examine the relationship between various heating rates and the permeabilities of the samples obtained at various rates, permeability measurements were performed using the samples respectively having the compositions shown in Tables 2 through 5. Table 2 shows the measurement results of the sample permeability when the heating rate was 0.5.degree. C./min. Table 3 shows the measurement results of the sample permeability when the heating rate was 5.degree. C./min. Table 4 shows the measurement results of the sample permeability when the heating rate was 80.degree. C./min. Table 5 shows the measurement results of the sample permeability when the heating rate was 160.degree. C./min. The other measurement conditions were the same as those of the above-described measurements. In the Tables, Ta indicates the heat treating temperature.
TABLE 1__________________________________________________________________________Heating Fe.sub.90 Zr.sub.7 B.sub.3 Fe.sub.89 Zr.sub.7 B.sub.4 Fe.sub.89 Zr.sub.6 B.sub.5 Fe.sub.89 Zr.sub.7 B.sub.4 Fe.sub.84 Zr.sub.7 B.sub.9range (.degree.C./m) M (1 kHz)__________________________________________________________________________0.5 1800 4500 55001.5 5100 8800 121002.5 5000 11700 143005 6800 5600 13600 1750010 7400 9200 13400 2300040 15100 10900 21500 17300100 19000 20600 23500200 22000 15000 18400 32000 24000__________________________________________________________________________
TABLE 2______________________________________Sample No. Alloy composition (at %) Ta(.degree.C.) .mu.(1 kHz)______________________________________1 Fe.sub.91 Zr.sub.7 B.sub.2 650 21002 Fe.sub.90 Zr.sub.7 B.sub.2 650 18003 (Fe.sub.99.5 Co.sub.0.5).sub.90 Zr.sub.7 B.sub.3 650 18104 (Fe.sub.99 Co.sub.1).sub.90 Zr.sub.7 B.sub.3 650 22505 (Fe.sub.98.5 Co.sub.1.5).sub.90 Zr.sub.7 B.sub.3 650 18406 (Fe.sub.98 Co.sub.2).sub.90 Zr.sub.7 B.sub.3 650 17807 (Fe.sub.95 Co.sub.5).sub.90 Zr.sub.7 B.sub.3 650 16908 (Fe.sub.99.5 Ni.sub.0.5).sub.90 Zr.sub.7 B.sub.3 600 14509 (Fe.sub.95 Ni.sub.5).sub.90 Zr.sub.7 B.sub.3 600 190010 Fe.sub.89 Zr.sub.7 B.sub.3 Cu.sub.1 600 1450011 Fe.sub.89 Zr.sub.7 B.sub.3 Ru.sub.1 600 176012 Fe.sub.89.5 Zr.sub.7 B.sub.3 Pd.sub.0.5 650 240013 Fe.sub.89 Zr.sub.7 B.sub.3 Pd.sub.1 650 501014 (Fe.sub.99 Co.sub.1).sub.84 Nb.sub.7 B.sub.9 650 585015 (Fe.sub.95 Co.sub.5).sub.84 Nb.sub.7 B.sub.9 650 467016 (Fe.sub.99 Ni.sub.1).sub.84 Nb.sub.7 B.sub.9 650 516017 Fe.sub.81 Ti.sub.7 B.sub.11 Cu.sub.1 600 730018 Fe.sub.81 Ta.sub.7 B.sub.11 Cu.sub.1 600 662019 Fe.sub.87 Ti.sub.1 Zr.sub.2 Hf.sub.2 V.sub.1 Nb.sub.1 B.sub.6 600 372020 Fe.sub.89 Zr.sub.7 B.sub.3 Bi.sub.1 600 152021 (Fe.sub.99 Ni.sub.1).sub.90 Zr.sub.7 B.sub.3 600 1590______________________________________ Heating-rate: 0.5.degree. C./m Shape of sample: Ring (inner diameter 6 mm, outer diameter 10 mm) Measured magnetic field: 5 mOe
TABLE 3______________________________________Sample No. Alloy composition (at %) Ta(.degree.C.) .mu.(1 kHz)______________________________________22 Fe.sub.91 Zr.sub.7 B.sub.2 650 470023 Fe.sub.90 Zr.sub.7 B.sub.2 650 680024 (Fe.sub.99.5 Co.sub.0.5).sub.90 Zr.sub.7 B.sub.3 650 400025 (Fe.sub.99 Co.sub.1).sub.90 Zr.sub.7 B.sub.3 650 410026 (Fe.sub.98.5 Co.sub.1.5).sub.90 Zr.sub.7 B.sub.3 650 470027 (Fe.sub.98 Co.sub.2).sub.90 Zr.sub.7 B.sub.3 650 500028 (Fe.sub.95 Co.sub.5).sub.90 Zr.sub.7 B.sub.3 650 440029 (Fe.sub.99.5 Ni.sub.0.5).sub.90 Zr.sub.7 B.sub.3 600 610030 (Fe.sub.95 Ni.sub.5).sub.90 Zr.sub.7 B.sub.3 600 790031 Fe.sub.89 Zr.sub.7 B.sub.3 Cu.sub.1 600 2040032 Fe.sub.89 Zr.sub.7 B.sub.3 Ru.sub.1 600 560033 Fe.sub.89.5 Zr.sub.7 B.sub.3 Pd.sub.0.5 650 740034 Fe.sub.89 Zr.sub.7 B.sub.3 Pd.sub.1 650 930035 (Fe.sub.99 Co.sub.1).sub.84 Nb.sub.7 B.sub.9 650 910036 (Fe.sub.95 Co.sub.5).sub.84 Nb.sub.7 B.sub.9 650 501037 (Fe.sub.99 Ni.sub.1).sub.84 Nb.sub.7 B.sub.9 650 790038 Fe.sub.81 Ti.sub.7 B.sub.11 Cu.sub.1 600 810039 Fe.sub.81 Ta.sub.7 B.sub.11 Cu.sub.1 600 820040 Fe.sub.87 Ti.sub.1 Zr.sub.2 Hf.sub.2 V.sub.1 Nb.sub.1 B.sub.6 600 550041 Fe.sub.89 Zr.sub.7 B.sub.3 Bi.sub.1 600 560042 (Fe.sub.99 Ni.sub.1).sub.90 Zr.sub.7 B.sub.3 600 6800______________________________________ Heating-rate: 5.degree. C./m Shape of sample: Ring (inner diameter 6 mm, outer diameter 10 mm) Measured magnetic field: 5 mOe
TABLE 4______________________________________Sample No. Alloy composition (at %) Ta(.degree.C.) .mu.(1 kHz)______________________________________43 Fe.sub.91 Zr.sub.7 B.sub.2 650 1790044 Fe.sub.90 Zr.sub.7 B.sub.2 650 1920045 (Fe.sub.99.5 Co.sub.0.5).sub.90 Zr.sub.7 B.sub.3 650 2430046 Fe.sub.99 Co.sub.1).sub.90 Zr.sub.7 B.sub.3 650 1730047 (Fe.sub.98.5 Co.sub.1.5).sub.90 Zr.sub.7 B.sub.3 650 1810048 (Fe.sub.98 Co.sub.2).sub.90 Zr.sub.7 B.sub.3 650 1840049 (Fe.sub.95 Co.sub.5).sub.90 Zr.sub.7 B.sub.3 650 822050 (Fe.sub.99.5 Ni.sub.0.5).sub.90 Zr.sub.7 B.sub.3 600 2800051 (Fe.sub.95 Ni.sub.5).sub.90 Zr.sub.7 B.sub.3 600 904052 Fe.sub.89 Zr.sub.7 B.sub.3 Cu.sub.1 600 4520053 Fe.sub.89 Zr.sub.7 B.sub.3 Ru.sub.1 600 1620054 Fe.sub.89.5 Zr.sub.7 B.sub.3 Pd.sub.0.5 650 1770055 Fe.sub.89 Zr.sub.7 B.sub.3 Pd.sub.1 650 2080056 (Fe.sub.99 Co.sub.1).sub.84 Nb.sub.7 B.sub.9 650 1470057 (Fe.sub.95 Co.sub.5).sub.84 Nb.sub.7 B.sub.9 650 852058 (Fe.sub.99 Ni.sub.1).sub.84 Nb.sub.7 B.sub.9 650 1480059 Fe.sub.81 Ti.sub.7 B.sub.11 Cu.sub.1 600 1650060 Fe.sub.81 Ta.sub.7 B.sub.11 Cu.sub.1 600 1450061 Fe.sub.87 Ti.sub.1 Zr.sub.2 Hf.sub.2 V.sub.1 Nb.sub.1 B.sub.6 600 913062 Fe.sub.89 Zr.sub.7 B.sub.3 Bi.sub.1 600 1650063 (Fe.sub.99 Ni.sub.1).sub.90 Zr.sub.7 B.sub.3 600 23400______________________________________ Heating-rate: 80.degree. C./m Shape of sample: Ring (inner diameter 6 mm, outer diameter 10 mm) Measured magnetic field: 5 mOe
TABLE 5______________________________________Sample No. Alloy composition (at %) Ta(.degree.C.) .mu.(1 kHz)______________________________________64 Fe.sub.91 Zr.sub.7 B.sub.2 650 1870065 Fe.sub.90 Zr.sub.7 B.sub.2 650 2410066 (Fe.sub.99.5 Co.sub.0.5).sub.90 Zr.sub.7 B.sub.3 650 2700067 Fe.sub.99 Co.sub.1).sub.90 Zr.sub.7 B.sub.3 650 2210068 (Fe.sub.98.5 Co.sub.1.5).sub.90 Zr.sub.7 B.sub.3 650 2330069 (Fe.sub.98 Co.sub.2).sub.90 Zr.sub.7 B.sub.3 650 1960070 (Fe.sub.95 Co.sub.5).sub.90 Zr.sub.7 B.sub.3 650 1030071 (Fe.sub.99.5 Ni.sub.0.5).sub.90 Zr.sub.7 B.sub.3 600 1730072 (Fe.sub.95 Ni.sub.5).sub.90 Zr.sub.7 B.sub.3 600 1870073 Fe.sub.89 Zr.sub.7 B.sub.3 Cu.sub.1 600 4420074 Fe.sub.89 Zr.sub.7 B.sub.3 Ru.sub.1 600 1980075 Fe.sub.89.5 Zr.sub.7 B.sub.3 Pd.sub.0.5 650 2200076 Fe.sub.89 Zr.sub.7 B.sub.3 Pd.sub.1 650 2240077 (Fe.sub.99 Co.sub.1).sub.84 Nb.sub.7 B.sub.9 650 1830078 (Fe.sub.95 Co.sub.5).sub.84 Nb.sub.7 B.sub.9 650 975079 (Fe.sub.99 Ni.sub.1).sub.84 Nb.sub.7 B.sub.9 650 1610080 Fe.sub.81 Ti.sub.7 B.sub.11 Cu.sub.1 600 1680081 Fe.sub.81 Ta.sub.7 B.sub.11 Cu.sub.1 600 1650082 Fe.sub.87 Ti.sub.1 Zr.sub.2 Hf.sub.2 V.sub.1 Nb.sub.1 B.sub.6 600 1080083 Fe.sub.89 Zr.sub.7 B.sub.3 Bi.sub.1 600 1890084 (Fe.sub.99 Ni.sub.1).sub.90 Zr.sub.7 B.sub.3 600 19200______________________________________ Heating-rate: 160.degree. C./m Shape of sample: Ring (inner diameter 6 mm, outer diameter 10 mm) Measured magnetic field: 5 mOe
It is clear from the measurement results shown in Tables 1 through 5 and FIG. 2 that the permeability of the soft magnetic alloy samples greatly depends on the heating rate in the heat treatment, and that as the greater the heating rate, the higher the permeability. Thus, we came to the conclusion from the measurement results shown in Tables 1 through 5 and FIG. 2 that the heating rate must be 1.0.degree. C./min or above in order to maintain permeability to 5000 or above.
In the subsequent examples, we measured the effective permeability (.mu.e) under conditions of 10 mOe and 1 kHz. measured the coercive force (Hc) with a d.c. B-H loop tracer. We calculated the saturation magnetization (Bs) from the magnetization measured under the conditions of 10 kOe by VSM.
In Examples 2 through 6, the magnetic characteristics shown are those of the alloys which have been subjected to water quenching after heating at a temperature of 600.degree. C. or 650.degree. C. for an hour. The magnetic characteristics shown in Examples 7 through 17 are those of the alloys which have been subjected to heating at a temperature ranging from 500.degree. to 700.degree. C. for an hour. The heating rate was between 80.degree. and 100.degree. C./min.
EXAMPLE 2
Regarding the effect of the heat treatment on the magnetic characteristics and structure of the alloy described in the above-described composition 1, those of the Fe.sub.90 Zr.sub.7 B.sub.3 alloy, one of the basic compositions, will be described below.
The crystallization initiation temperature of the Fe.sub.90 Zr.sub.7 B.sub.3 alloy, obtained by the differential thermal analysis at a heating rate of 10.degree. C./min, was 480.degree. C.
FIG. 3 is a graphic illustration showing the effect of annealing (retained for an hour at each temperature) on the effective permeability of the Fe.sub.90 Zr.sub.7 B.sub.3 alloy. It is clear from FIG. 3 that the effective permeability of the alloy according to the present invention, which decreases as the annealing temperature decreases, increases rapidly due to the annealing at a temperature of 500.degree. to 650.degree. C.
We investigated frequency dependency of the permeability of a 20 .mu.m-thick sample which was subjected to the heat treatment at 650.degree. C., and found the sample exhibited excellent soft magnetic characteristics at high frequencies, like 26500 at 1 kHz, 19800 at 10 kHz and 7800 at 100 kHz.
We investigated changes in the structure of the Fe.sub.90 Zr.sub.7 B.sub.3 alloy, caused by the heat treatment, by the X-ray diffraction method. Also, we observed the structure of the heat treated alloy using a transmission type electronic microscope. The results are shown in FIGS. 4 and 5, respectively.
As shown in FIG. 4, the haloed diffraction pattern characteristic to the amorphous phase is observed in a quenched state, while the diffraction pattern inherent in the body-centered cubic structure is observed after heat treatment. It is thus clear that the structure of the alloy according to the present invention changed from the amorphous phase to the body-centered cubic structure as a consequence of the heat treatment.
It is also clear from the results of the structure observation shown in FIG. 5 that the heat treated structure was composed of fine grains having a grain size of about 100 to 200 .ANG. (10 to 20 nm).
We examined changes in the hardness of the Fe.sub.90 Zr.sub.7 B.sub.3 alloy, caused by the heat treatment, and found that the hardness increased from 750 DPN, Vickers hardness obtained in a quenched state, to a high value of 1400 DPN which cannot be conventionally obtained, after the heat treatment.
It is therefore clear that the structure mainly composed of super fine grains, obtained by heat treating and thereby crystallizing the amorphous alloy having the aforementioned composition, exhibits high saturation magnetization, excellent soft magnetic characteristics, a high hardness and high thermal stability.
Further, the present inventors examined how the magnetic characteristics of the alloy changed when the proportion of Zr and that of B in the alloy were varied. Table 6 and FIGS. 6 through 9 show the magnetic characteristics of the annealed alloy.
TABLE 6__________________________________________________________________________ Alloy Heat SaturationSample composition treatment Permeability magnetizationNo. (at %) .degree.Clh .mu.(1 KHz) Bs(G)__________________________________________________________________________85 Fe.sub.91 Zr.sub.8 B.sub.1 600 12384 1670086 Fe.sub.91 Zr.sub.9 600 1056 16500 (Comparative example)87 Fe.sub.89 Zr.sub.5 B.sub.6 600 24384 1700088 Fe.sub.87 Zr.sub.5 B.sub.8 600 10829 1600089 Fe.sub.87 Zr.sub.3 B.sub.10 600 296 1720090 Fe.sub.87 B.sub.13 600 192 18000 (Comparative91 Fe.sub.81 Zr.sub.7 B.sub.12 600 230 12900 example)92 Fe.sub.85 Zr.sub.11 B.sub.4 600 2 900093 Fe.sub.91 Zr.sub.7 B.sub.2 600 24384 1660094 Fe.sub.89 Zr.sub.7 B.sub.4 600 20554 1600095 Fe.sub.92 Zr.sub.7 B.sub.1 600 17184 1710096 Fe.sub.90 Zr.sub.7 B.sub.3 600 23808 1660097 Fe.sub.88 Zr.sub.7 B.sub.5 600 8794 1550098 Fe.sub.91 Zr.sub.6 B.sub.3 600 19776 1710099 Fe.sub.90 Zr.sub.6 B.sub.4 600 22464 17000100 Fe.sub.90 Zr.sub.8 B.sub.2 600 10944 15900101 Fe.sub.89 Zr.sub.8 B.sub.3 600 8083 15400__________________________________________________________________________ Heating-rate: 80.degree. C./min to 100.degree. C./min
It is clear from Table 6 and FIGS. 6 through 9 that high permeability and high saturation magnetization can be readily obtained when the proportion of Zr is between 4 and 9 atomic percent. It is also clear that effective permeability was not increased to 5000 or above, preferably, 10000 or above when the proportion of Zr is less than 4 atomic percent and that permeability rapidly decreases and saturation magnetization decreases when the proportion of Zr exceeds 9 atomic percent. Hence, the present inventors limited the proportion of Zr contained in the alloy having any of compositions 1 through 4 to between 4 and 9 atomic percent.
Similarly, when the proportion of B is between 0.5 and 10 atomic percent, effective permeability can be readily increased to 5000 or above, preferably, to 10000 or above. Consequently, the present inventors limited the proportion of B to between 0.5 and 10 atomic percent. Further, even when the proportion of Zr and that of B are within the above range, high permeability cannot be obtained if the proportion of Fe exceeds 93 atomic percent. Thus, the present inventors limited the proportion of Fe to 93 atomic percent or below in the alloy used in the present invention.
EXAMPLE 3
A Fe--Hf--B alloy system, obtained by substituting Hf for Zr in the Fe--Zr--B alloy system shown in Example 2, will be described.
Table 7 shows the magnetic characteristics obtained when the proportion of Hf in the Fe--Hf--B alloy system is changed from 4 to 9 atomic percent.
TABLE 7______________________________________ Alloy SaturationSample composition Permeability magnetizationNo. (at %) .mu.(1 KHz) Bs(G)______________________________________102 Fe.sub.88 Hf.sub.4 B.sub.6 8200 16200103 Fe.sub.89 Hf.sub.5 B.sub.6 17200 16000104 Fe.sub.90 Hf.sub.6 B.sub.4 24800 15500105 Fe.sub.89 Hf.sub.7 B.sub.4 28000 15000106 Fe.sub.88 Hf.sub.8 B.sub.4 25400 14500107 Fe.sub.87 Hf.sub.9 B.sub.4 12100 14000108 Fe.sub.91 Zr.sub.4 Hf.sub.3 B.sub.2 27800 16500______________________________________
It is apparent from the characteristics shown in Table 7 that the effective permeability of the Fe--Hf--B alloy system is equivalent to that of the Fe--Zr--B alloy system when the proportion of Hf is between 4 and 9 atomic percent.
Further, the magnetic characteristics of the Fe.sub.91 Zr.sub.4 Hf.sub.3 B.sub.2 alloy shown in Table 7 are the same as those of Fe--Zr--B alloy system of Example 2. Thus, it is clear that Zr in the Fe--Zr--B alloy system shown in Example 2 can be replaced by Hf partially or entirely in its limited composition range from 4 to 9 atomic percent.
EXAMPLE 4
An alloy in which part of Zr and/or Hf of Fe--(Zr, Hf)--B alloy system, shown in Examples 2 and 3, is replaced by Nb will now be described.
Table 8 shows the magnetic characteristics of the alloys in which part of Zr of the Fe--Zr--B alloy system has been replaced by 1 to 5 atomic percent of Nb.
TABLE 8__________________________________________________________________________ Alloy SaturationSample composition Permeability magnetizationNo. (at %) .mu.(1 KHz) Bs(G)__________________________________________________________________________109 Fe.sub.90 Zr.sub.6 Nb.sub.1 B.sub.6 21000 16600110 Fe.sub.89 Zr.sub.5 Nb.sub.2 B.sub.4 14000 16200111 Fe.sub.88 Zr.sub.6 Nb.sub.2 B.sub.4 12500 15400112 Fe.sub.87 Zr.sub.7 Nb.sub.2 B.sub.4 7600 14500113 Fe.sub.86 Zr.sub.8 Nb.sub.2 B.sub.4 2300 14000 (Comparative example)114 Fe.sub.89 Zr.sub.6 Nb.sub.3 B.sub.2 8200 15900115 Fe.sub.88 Zr.sub.6 Nb.sub.4 B.sub.2 4100 14500 (Comparative example)116 Fe.sub.87 Zr.sub.6 Nb.sub.5 B.sub.2 1800 14000 (Comparative example)117 Fe.sub.86 Ni.sub.1 Zr.sub.4 Nb.sub.3 B.sub.6 17900 15400__________________________________________________________________________
It is clear from Table 8 that the proportion of Zr+Nb assuring high permeability is between 4 and 9 atomic percent, as in the case of Zr in the Fe--Zr--B alloy system) and that the inclusion of Nb has the same effect as that of Zr. Therefore, it is clear that part of Zr, Hf in the Fe--(Zr, Hf)--B alloy system can be replaced by Nb.
EXAMPLE 5
An alloy in which Nb in the Fe--(Zr, Hf)--Nb--B alloy system is replaced by Ti, V, Ta, Mo or W will be described.
Table 9 shows the magnetic characteristics of the Fe--Zr--M'--B (M' is either of Ti, V, Ta, Mo or W) alloy system.
TABLE 9__________________________________________________________________________ Alloy SaturationSample composition Permeability magnetizationNo. (at %) (1 KHz) Bs(G)__________________________________________________________________________118 Fe.sub.89 Zr.sub.6 Ti.sub.2 B.sub.3 12800 15800119 Fe.sub.89 Zr.sub.6 V.sub.2 B.sub.3 11100 15800120 Fe.sub.89 Zr.sub.6 Ta.sub.2 B.sub.3 15600 15200121 Fe.sub.89 Zr.sub.6 Mo.sub.2 B.sub.3 12800 15300122 Fe.sub.89 Zr.sub.6 W.sub.2 B.sub.3 13100 15100123 Fe--Si--B 5000 14100 Amorphous alloy124 Silicon steel (Si 6.5 wt %) 2400 18000125 Fe--Si--Al alloy 20000 11000126 Fe--Ni alloy 15000 8000 (Comparative example) (Permalloy)127 Co--Fe--Si--B 65000 8000 Amorphous alloy__________________________________________________________________________
In Table 9, the effective permeability of the alloys according to the present invention is higher than 5000, which is the effective permeability of a comparative example of a Fe-based amorphous alloy (sample No. 123) and that of a comparative example of a silicon steel (sample No. 124), while the saturation magnetization thereof is better than that of a Fe--Si--Al alloy (sample No. 125), that of a Fe--Ni alloy (sample No. 126) or that of a Co-based amorphous alloy (sample No. 127). It is thus clear from Table 9 that the alloys according to the present invention exhibit both excellent permeability and excellent saturation magnetization, and that Nb in the Fe--(Zr, Hf)Nb--B alloy system can be replaced by Ti, V, Ta, Mo or W.
EXAMPLE 6
The reasons for limiting the proportion of Co and that of Ni to those described in the above-described compositions will be described below.
FIG. 10 shows the relationship between the proportion of Co and that of Ni (a) in the alloy having a composition expressed by (Fe.sub.1-a Z.sub.a).sub.91 Zr.sub.7 B.sub.2 (Z.dbd.Co, Ni) and permeability thereof.
It is apparent from the results shown in FIG. 10 that effective permeability is increased to 5000 or above, which is higher than that of the Fe-based amorphous alloy, when the proportion of Co or Ni (a) is 0.1 or below, while effective permeability rapidly decreases when the proportion of Co or Ni exceeds 0.1. Thus, the present inventors limited the proportion of Co and that of Ni (a) in the alloys described in the above composition to 0.1 or below. In order to obtain effective permeability of 10000 or above, a more preferable a is 0.05 or below.
EXAMPLE 7
Regarding the effect of the heat treatment on the magnetic characteristics and structure of the alloys having composition examples 9 through 12, those of the Fe.sub.86 Zr.sub.7 B.sub.6 Cu.sub.1 alloy, one of the basic compositions, will be described below.
The crystallization initiation temperature of the Fe.sub.86 Zr.sub.7 B.sub.6 Cu.sub.1 alloy, obtained by the differential thermal analysis at a heating rate of 10.degree. C./min, was 503.degree. C.
FIG. 11 is a graphic illustration showing the effect of annealing (retained for an hour at each temperature) on the effective permeability of the Fe.sub.86 Zr.sub.7 B.sub.6 Cu.sub.1 alloy.
It is clear from FIG. 11 that the effective permeability of the alloy according to the present invention in a quenched state (RQ), which is as low as that of the Fe-based amorphous alloy, increases to a value which is about ten times that of the value in the quenched state, due to the annealing at a temperature ranging from 500.degree. to 620.degree. C. We investigated frequency dependency of the permeability of a 20 .mu.m-thick sample which was subjected to the heat treatment at 650.degree. C., and found the sample exhibited excellent soft magnetic characteristics at high frequencies, like 32000 at 1 kHz, 25600 at 10 kHz and 8330 at 100 kHz.
The magnetic characteristics of the alloy used in the present invention can be adjusted by adequately selecting the heat treating conditions, such as the heating rate, and improved by, for example, annealing in a magnetic field.
We investigated changes in the structure of the Fe.sub.86 Zr.sub.7 B.sub.6 Cu.sub.1 alloy, caused by the heat treatment, by the X-ray diffraction method. Also, we observed the structure of the heat treated alloy using a transmission type electronic microscope. The results are shown in FIGS. 12 and 13, respectively.
As shown in FIG. 12, the haloed diffraction pattern characteristic to the amorphous phase is observed in a quenched state, while the diffraction pattern inherent in the body-centered cubic structure is observed after heat treatment. It is thus clear that the structure of the alloy according to the present invention changed from the amorphous phase to the body-centered cubic structure as a consequence of the heat treatment.
It is also clear from the transmission electronic microscopic photograph of the metallic structure shown in FIG. 13 that the heat treated structure is composed of fine grains having a grain size of about 100 .ANG. (10 nm).
We examined changes in the hardness of the Fe.sub.86 Zr.sub.7 B.sub.6 Cu.sub.1 alloy, caused by the heat treatment, and found that the hardness increased from 740 DPN, Vickers hardness obtained in a quenched state, to 1390 DPN which cannot be obtained in conventional amorphous materials, after the heat treatment.
It is therefore clear that the structure mainly composed of super fine grains, obtained by heat treating and thereby crystallizing the amorphous alloy having the aforementioned composition, exhibits high saturation magnetization, excellent soft magnetic characteristics, a high hardness and high thermal stability.
The present inventors examined how the magnetic characteristics of the alloy having composition examples 9 and 11 changed when the proportion of Zr and that of B in the alloy were varied. Table 10 and FIG. 14 show the magnetic characteristics of the annealed alloy.
TABLE 10______________________________________ Alloy CoerciveSample composition Permeability force magnetizationNo. (at %) .mu.e (1 K) Hc(Oe) Bs(KG)______________________________________128 Fe.sub.85 Zr.sub.4 B.sub.10 Cu.sub.1 9250 0.150 14.9129 Fe.sub.83 Zr.sub.4 B.sub.12 Cu.sub.1 7800 0.170 14.2130 Fe.sub.88 Zr.sub.5 B.sub.6 Cu.sub.1 15500 0.190 16.7131 Fe.sub.86 Zr.sub.5 B.sub.8 Cu.sub.1 23200 0.032 15.2132 Fe.sub.84 Zr.sub.5 B.sub.10 Cu.sub.1 21100 0.055 14.5133 Fe.sub.82 Zr.sub.5 B.sub.12 Cu.sub.1 12000 0.136 13.9134 Fe.sub.89 Zr.sub.6 B.sub.4 Cu.sub.1 30300 0.038 17.0135 Fe.sub.88 Zr.sub.6 B.sub.5 Cu.sub.1 15200 0.052 16.3136 Fe.sub.87 Zr.sub.6 B.sub.6 Cu.sub.1 18300 0.040 15.7137 Fe.sub.86 Zr.sub.6 B.sub.7 Cu.sub.1 15400 0.042 15.2138 Fe.sub.91 Zr.sub.7 B.sub.1 Cu.sub.1 20700 0.089 17.1139 Fe.sub.90 Zr.sub.7 B.sub.2 Cu.sub.1 32200 0.030 16.8140 Fe.sub.89 Zr.sub.7 B.sub.3 Cu.sub.1 32400 0.036 16.2141 Fe.sub.88 Zr.sub.7 B.sub.4 Cu.sub.1 31300 0.102 15.8142 Fe.sub.87 Zr.sub.7 B.sub.5 Cu.sub.1 31000 0.082 15.3143 Fe.sub.86 Zr.sub.7 B.sub.6 Cu.sub.1 32000 0.044 15.0144 Fe.sub.84 Zr.sub.7 B.sub.8 Cu.sub.1 25700 0.044 14.2145 Fe.sub.82 Zr.sub.7 B.sub.10 Cu.sub.1 19200 0.038 13.3146 Fe.sub.80 Zr.sub.7 B.sub.12 Cu.sub.1 23800 0.044 12.5147 Fe.sub.78 Zr.sub.7 B.sub.14 Cu.sub.1 13300 0.068 11.8148 Fe.sub.76 Zr.sub.7 B.sub.16 Cu.sub.1 10000 0.20 11.1149 Fe.sub.88 Zr.sub.8 B.sub.3 Cu.sub.1 29800 0.084 15.4150 Fe.sub.85 Zr.sub.8 B.sub.6 Cu.sub.1 28000 0.050 14.2151 Fe.sub.84 Zr.sub.8 B.sub.7 Cu.sub.1 20400 0.044 13.8152 Fe.sub.88 Zr.sub.9 B.sub.2 Cu.sub.1 11700 0.112 15.1153 Fe.sub.86 Zr.sub.9 B.sub.4 Cu.sub.1 12900 0.160 14.3154 Fe.sub.84 Zr.sub.9 B.sub.6 Cu.sub.1 11800 0.108 13.1155 Fe.sub.86 Zr.sub.10 B.sub.4 Cu.sub.1 6240 0.210 12.8156 Fe.sub.83 Zr.sub.10 B.sub.6 Cu.sub.1 5820 0.220 12.0______________________________________
It is clear from Table 10 and FIG. 14 that high permeability can be readily obtained when the proportion of Zr is between 4 and 10 atomic percent. It is also clear that effective permeability was not increased to more than 5000 to 10000 when the proportion of Zr is less than 4 atomic percent and that permeability rapidly decreases and saturation magnetization decreases when the proportion of Zr exceeds 10 atomic percent. Hence, the present inventors limited the proportion of Zr contained in the alloy according to the present invention to between 4 and 10 atomic percent.
Similarly, when the proportion of B is between 0.5 and 18 atomic percent, effective permeability can be readily increased to 5000 or above. Hence, the present inventors limited the proportion of B to between 0.5 and 18 atomic percent.
Further, even when the proportion of Zr and that of B are within the above range, high permeability cannot be obtained if the proportion of Fe exceeds 93 atomic percent. Thus, the present inventors limited the proportion of Fe+Co (b) in the alloy having composition examples 9 and 11 to 93 atomic percent or below.
EXAMPLE 8
A Fe--Hf--B--Cu alloy system, obtained by substituting Hf for Zr in the Fe--Zr--B--Cu alloy system shown in Example 7, will be described.
Table 11 shows the magnetic characteristics of the alloys having various compositions in which the proportion of B is fixed to 6 atomic percent and the proportion of Cu is fixed to 1 atomic percent. FIG. 15 shows permeability obtained when the proportion of Hf is varied from 4 to 10 atomic percent. For comparison, the effective permeability of the Fe--Zr--B.sub.6 --Cu.sub.1 alloy system is also shown in FIG. 15.
TABLE 11______________________________________Sam- Perme- Coercive Saturationple Alloy composition ability force magnetizationNo. (atm %) .mu.(1 K) Hc(Oe) Bs(KG)______________________________________157 Fe.sub.89 Hf.sub.4 B.sub.6 Cu.sub.1 9350 0.150 16.1158 Fe.sub.88 Hf.sub.5 B.sub.6 Cu.sub.1 20400 0.048 15.7159 Fe.sub.87 Hf.sub.6 B.sub.6 Cu.sub.1 26500 0.028 15.2160 Fe.sub.86 Hf.sub.7 B.sub.6 Cu.sub.1 25200 0.028 14.7161 Fe.sub.85 Hf.sub.8 B.sub.8 Cu.sub.1 25200 0.038 14.1162 Fe.sub.84 Hf.sub.9 B.sub.6 Cu.sub.1 19600 0.068 13.5163 Fe.sub.83 Hf.sub..sub.10 B.sub.6 Cu.sub.1 9860 0.104 12.8164 Fe.sub.86 Zr.sub.4 Hf.sub.3 B.sub.6 Cu.sub.1 39600 0.032 14.8______________________________________
It is apparent from the characteristics shown in Table 11 and FIG. 15 that the effective permeability of the Fe--Hf--B--Cu alloy system is equivalent to that of the Fe--Zr--B--Cu alloy system when the proportion of Hf is between 4 and 9 atomic percent. Further, the magnetic characteristics of the Fe.sub.86 Zr.sub.4 Hf.sub.3 B.sub.6 Cu.sub.1 alloy shown in Table 11 are the same as those of Fe--Zr--B--Cu alloy system of Example 7. Thus, it is clear that Zr in the Fe--Zr--B--Cu alloy system shown in Example 7 can be replaced by Hf partially or entirely within its limited composition range from 4 to 10 atomic percent.
EXAMPLE 9
A case in which part of the Zr and/or Hf of Fe--(Zr, Hf)--B--Cu alloy system, shown in Examples 7 and 8, is replaced by Nb will now be described.
Table 12 shows the magnetic characteristics of the alloys in which part of Zr of the Fe--Zr--B--Cu alloy system has been replaced by 1 to 5 atomic percentage of Nb. FIG. 16 shows the magnetic characteristics of the Fe--Zr--Nb--B--Cu alloy system in which the proportion of Nb is 3 atomic percent.
TABLE 12______________________________________ Perme- Coercive SaturationSample Alloy composition ability force magnetizationNo. (at %) .mu.(1K) Hc(Oe) Bs(KG)______________________________________165 Fe.sub.88 Zr.sub.4 Nb.sub.1 B.sub.6 Cu.sub.1 11300 0.108 16.9166 Fe.sub.87 Zr.sub.4 Nb.sub.2 B.sub.6 Cu.sub.1 37400 0.042 15.9167 Fe.sub.86 Zr.sub.4 Nb.sub.4 B.sub.6 Cu.sub.1 35700 0.046 15.3168 Fe.sub.85 Zr.sub.4 Nb.sub.4 B.sub.6 Cu.sub.1 30700 0.050 14.3169 Fe.sub.84 Zr.sub.4 Nb.sub.5 B.sub.6 Cu.sub.1 14600 0.092 13.7170 Fe.sub.86 Zr.sub.2 Nb.sub.3 B.sub.8 Cu.sub.1 14900 0.108 16.6171 Fe.sub.84 Zr.sub.2 Nb.sub.3 B.sub.10 Cu.sub.1 15900 0.085 16.2172 Fe.sub.87 Zr.sub.3 Nb.sub.3 B.sub.6 Cu.sub.1 33800 0.048 16.0173 Fe.sub.85 Zr.sub.3 Nb.sub.3 B.sub.8 Cu.sub.1 24100 0.095 15.5174 Fe.sub.88 Zr.sub.4 Nb.sub.3 B.sub.4 Cu.sub.1 16900 0.076 15.6175 Fe.sub.84 Zr.sub.4 Nb.sub.3 B.sub.8 Cu.sub.1 38700 0.038 14.6176 Fe.sub.86 Zr.sub.5 Nb.sub.3 B.sub.5 Cu.sub.1 24200 0.048 14.8177 Fe.sub.84 Zr.sub.5 Nb.sub.3 B.sub.7 Cu.sub.1 21700 0.038 14.0178 Fe.sub.84 Zr.sub.8 Nb.sub.3 B.sub.6 Cu.sub.1 17300 0.110 13.9179 Fe.sub.82 Zr.sub.6 Nb.sub.3 B.sub.8 Cu.sub.1 20400 0.045 13.2180 Fe.sub.79 Zr.sub.7 Nb.sub.3 B.sub.10 Cu.sub.1 10800 0.125 12.4______________________________________
It is clear from Table 12 and FIG. 16 that the proportion of Zr+Nb assuring high permeability is between 4 and 10 atomic percent, as in the case of Zr in the Fe--Zr--Cu alloy system, and that the inclusion of Nb in the above range assures effective permeability as high as that of the Fe--Zr--B--Cu alloy system. Therefore, it is clear that part of Zr, Hf in the Fe--(Zr, Hf)--Cu alloy system can be replaced by Nb.
EXAMPLE 10
A case in which Nb in the Fe--(Zr, Hf)--Nb--B--Cu alloy is replaced by Ti, V, Ta, Mo or W will be described.
Table 13 shows the magnetic characteristics of the Fe--Zr--M'--B--Cu.sub.1 (M' is either of Ti, V, Ta, Mo and W) alloy system.
TABLE 13______________________________________ Perme- Coercive SaturationSample Alloy composition ability force magnetizationNo. (at %) .mu.(1K) Hc(Oe) Bs(KG)______________________________________181 Fe.sub.80 Zr.sub.1 Ti.sub.6 B.sub.12 Cu.sub.1 13800 0.105 12.8182 Fe.sub.86 Zr.sub.4 Ti.sub.3 B.sub.6 Cu.sub.1 12700 0.110 14.7183 Fe.sub.84 Zr.sub.4 V.sub.5 B.sub.6 Cu.sub.1 6640 0.201 13.5184 Fe.sub.86 Zr.sub.4 To.sub.3 B.sub.6 Cu.sub.1 20900 0.096 15.1185 Fe.sub.84 Zr.sub.4 To.sub.5 B.sub.6 Cu.sub.1 8310 0.172 14.0186 Fe.sub.86 Zr.sub.4 Mo.sub.3 B.sub.6 Cu.sub.1 9410 0.160 15.3187 Fe.sub.84 Zr.sub.4 Mo.sub.5 B.sub.6 Cu.sub.1 9870 0.160 13.7188 Fe.sub.86 Zr.sub.4 W.sub.3 B.sub.6 Cu.sub.1 11700 0.098 14.8189 Fe.sub.84 Zr.sub.4 W.sub.5 B.sub.6 Cu.sub.1 6910 0.211 13.2______________________________________
In Table 13, the effective permeability of the alloys shown in Table 13 is higher than 5000, which is the effective permeability of a Fe-based amorphous alloy. It is thus clear that Nb in the Fe--(Zr, Hf)Nb--B--Cu alloy system can be replaced by Ti, V, Ta, Mo or W.
EXAMPLE 11
The reasons for limiting the proportion of Cu to that described in the above-described compositions 9 and 11 will be described below.
FIG. 17 shows the relationship between the proportion of Cu (x) in the alloy having a composition expressed by Fe.sub.87-x Zr.sub.4 Nb.sub.3 B.sub.6 Cu.sub.x and permeability.
It is apparent from the results shown in FIG. 17 that effective permeability of 10000 or above can be obtained when x=0.2 to 4.5 atomic percent. When x is less than 0.2 atomic percent, the effect of the addition of Cu is not obvious. When x is more than 4.5 atomic percents, the permeability of the alloy deteriorates. Therefore, the addition of more than 4.5 atomic percent of Cu is not practical. However, even when x is less than 0.2 atomic percent, effective permeability of 5000 or above can be obtained and the saturation magnetization improves due to an increase in the proportion of Fe resulting from a reduction in the proportion of Cu. Thus, the proportion of Cu may also be between 0 and 0.2 atomic percent. Consequently, the present inventors limited the proportion of Cu in the alloys described in the above compositions 9 and 11 to 4.5 atomic percent or below.
EXAMPLE 12
A case in which Cu in the alloys having compositions 7 through 11 is replaced by Ag, Ni, Pd or Pt will be described.
Table 14 shows the magnetic characteristics of the Fe.sub.86 Zr.sub.4 Nb.sub.3 B.sub.6 T.sub.1 (T=Ag, Au, Pd, Pt) alloy.
TABLE 14______________________________________ Perme- Coercive SaturationSample Alloy composition ability force magnetizationNo. (at %) .mu.(1K) Hc(Oe) Bs(KG)______________________________________190 Fe.sub.86 Zr.sub.4 Nb.sub.3 B.sub.6 Pd.sub.1 18800 0.064 15.4191 Fe.sub.86 Zr.sub.4 Nb.sub.3 B.sub.6 Pt.sub.1 19900 0.096 14.8192 Fe.sub.86 Zr.sub.4 Nb.sub.3 B.sub.6 Ag.sub.1 17800 0.090 15.3193 Fe.sub.86 Zr.sub.4 Nb.sub.3 B.sub.6 Au.sub.1 21500 0.076 15.2______________________________________
It is clear from Table 14 that effective permeability of 10000 or above can be obtained, i.e., the magnetic characteristics as excellent as those of Cu can be obtained. It is thus apparent that Cu in the alloys having compositions 9 and 11 is replaceable with Ag, Au, Pd or Pt.
EXAMPLE 13
The reasons for limitation of the proportion of Co in the alloy having composition 11 will be described.
FIG. 18 shows the relation between permeability and the proportion of Co (a) in the (Fe.sub.1-a Co.sub.a).sub.86 Zr.sub.4 Nb.sub.3 B.sub.6 Cu.sub.1.
It is apparent from FIG. 18 that when a is 0.1 or below, effective permeability of 5000 or above, which is higher than that of the Fe-type amorphous alloy, can be obtained. Thus, the present inventors limited the proportion of Co (a) in the alloy having composition 11 to 0.1 or below. In order to increase effective permeability to 10000 or above, a desirable proportion of Cu is 0.05 or below.
EXAMPLE 14
Regarding the effect of the heat treatment on the magnetic characteristics and structure of the alloys having compositions 13 through 16, those of the Fe.sub.80 Nb.sub.7 B.sub.12 Cu.sub.1 alloy, one of the basic compositions 13 to 16, will be described below.
The crystallization initiation temperature of the above alloy, obtained by the differential thermal analysis at a heating rate of 10.degree. C./min, was 470.degree. C. In the case of this composition, the addition of Nb is mandatory. The same magnetic characteristics as those obtained when Nb is added can be obtained even when part of Nb is replaced by Ti or Ta.
FIG. 19 is a graphic illustration showing the effect of annealing (retained for an hour at each temperature) on the effective permeability of the Fe.sub.80 Nb.sub.7 B.sub.12 Cu.sub.1 alloy.
It is clear from FIG. 19 that the effective permeability of the alloy according to the present invention in a quenched state (RQ), which is as low as that of the Fe-based amorphous alloy, increases to a value which is about ten times that of the value in the quenched state, due to the annealing at a temperature ranging from 500.degree. to 620.degree. C. We investigated the frequency dependency of the permeability of an approximately 20 .mu.m-thick sample which was subjected to the heat treatment at 600.degree. C., and found the sample exhibited excellent soft magnetic characteristics at high frequencies, like 28800 at 1 kHz, 25400 at 10 kHz and 7600 at 100 kHz.
FIG. 20 shows the results of the measurements regarding an influence of the proportion of B on the effective permeability of the Fe.sub.92-x Nb.sub.7 B.sub.x Cu.sub.1 alloy. In FIG. 20, we examined how permeability changed when the proportion of B was varied between 6 and 18 atomic percent.
It is clear from FIG. 20 that when the proportion of B is between 6.5 and 18 atomic percent, excellent permeability can be obtained. Thus, the present inventors limited the proportion of B to 6.5 to 18 atomic percent in the alloy having either of compositions 13 through 16.
EXAMPLE 15
FIG. 21 shows the results of the measurements conducted to examine an influence of the proportion of Nb on the effective permeability of the Fe.sub.87-x Nb.sub.x B.sub.12 Cu.sub.1 alloy. In the measurements shown FIG. 21, we examined how permeability changed when the proportion of Nb was varied between 3 and 11 atomic percent.
It is clear from FIG. 21 that when the proportion of Nb is between 4 and 10 atomic percent, excellent permeability can be obtained. Thus, the present inventors limited the proportion of Nb to 4 to 10 atomic percent in the alloy having either of compositions 9 through 16.
We investigated changes in the structure of the Fe.sub.92-x Nb.sub.7 B.sub.x Cu.sub.1 alloy, caused by the heat treatment, by the X-ray diffraction method. Also, we observed the structure of the heat treated alloy using a transmission type electronic microscope. The results are shown in FIGS. 22 and 23, respectively.
As shown in FIG. 22, the haloed diffraction pattern characteristic to the amorphous phase is observed in a quenched state, while the diffraction pattern inherent in the crystalline structure is observed after heat treatment. It is thus clear that the structure of the alloy according to the present invention changed from the amorphous phase to the crystalline structure as a consequence of the heat treatment.
It is also clear from FIG. 23 that the heat treated structure is composed of fine grains having a grain size of about 100 .ANG. (10 nm).
We examined changes in the hardness of the Fe.sub.80 Nb.sub.12 B.sub.7 Cu.sub.1 alloy, caused by the heat treatment, and found that the hardness increased from 650 DPN, Vickers hardness obtained in a quenched state, to 950 DPN, after the heat treatment.
In the alloy according to the present invention having any of the compositions 5 through 8 and 13 through 16, the structure mainly composed of super fine grains, obtained by heat treating and thereby crystallizing the amorphous alloy having any of the aforementioned compositions, exhibits high saturation magnetization, excellent soft magnetic characteristics, a high hardness and high thermal stability. Further, since the major elements employed in the alloy according to the present invention do not tend to readily generate an oxide and are thus not readily oxidized during manufacture, manufacture of the alloy is facilitated.
We measured changes in the permeability of the soft magnetic alloy according to the present invention having any of the compositions 13 through 16, caused by changes in the proportions of Fe+Cu, of B and of Nb. The results of the measurements are shown in FIG. 24.
It is clear from FIG. 24 that permeability of about 10000 can be obtained when the proportion of Nb is between 4 and 10 atomic percent and when the proportion of B is between 6.5 and 18 atomic percent.
We measured changes in the saturation magnetization of the soft magnetic alloy according to the present invention described in compositions 13 through 16, caused by changes in the proportions of Fe+Cu, of B and of Nb. The results of the measurements are shown in FIG. 25.
It is clear from FIG. 25 that excellent saturation magnetization of 13 kG to 16 kG can be obtained in the alloy composition range according to the present invention.
The reasons for limitation of the proportion of Cu in the alloy described in compositions 13 through 16 will be described below.
FIG. 26 shows the relation between the proportion of Cu (z) in the alloy having a composition expressed by Fe.sub.82.5-z Nb.sub.7 B.sub.10.5 Cu.sub.z and permeability.
It is apparent from the results shown in FIG. 26 that excellent effective permeability can be obtained when z=0.2 to 4.5 atomic percent. When z is less than 0.2 atomic percent, the effect of the addition of Cu is not obvious. When z is more than 4.5 atomic percent, the permeability of the alloy deteriorates. Therefore, the addition of more than 4 atomic percentage of Cu is not practical. However, when z is less than 0.2 atomic percent, practical effective permeability of 5000 or above can be obtained, and saturation magnetization can be slightly increased. Thus, the proportion of Cu may also be 0.2 atomic percent or below. Consequently, the present inventors limited the proportion of Cu in the alloy employed in the present invention to 4.5 atomic percent or below.
An alloy, such as a Fe--Nb--Ta--B--Cu alloy system, a Fe--Nb--Ti--B--Cu alloy system or a Fe--Nb--Ta--Ti--B--Cu alloy system, obtained by replacing Nb in the Fe--Nb--B--Cu alloy system by a plurality of elements, will be described.
FIG. 27 shows the permeability of the alloy in which Nb and part of Nb are respectively replaced by 4 to 10 atomic percent of Ta and 4 to 10 atomic percent of Ti with proportion of B and that of Cu fixed to 12 atomic percent and 1 atomic percent, respectively.
It is clear from the results shown in FIG. 27 that almost the same permeability is obtained in the alloys having various compositions.
Further, we measured the saturation magnetization (kG) of the alloy having compositions shown in Table 15.
TABLE 15______________________________________Alloy composition Saturation magnetic Permeability(atm %) flux density Bs(KG) .mu.(1 kHz)______________________________________Fe.sub.84 Nb.sub.7 B.sub.8 Cu.sub.1 15.3 (kG) 31000Fe.sub.80 Ta.sub.7 B.sub.12 Cu.sub.1 12.0 20000Fe.sub.82 Ti.sub.7 B.sub.10 Cu.sub.1 14.0 26000Fe.sub.82 Ta.sub.4 Ti.sub.3 B.sub.10 Cu.sub.1 14.0 24000Fe.sub.82 Nb.sub.3 Ta.sub.2 Ti.sub.2 B.sub.10 Cu.sub.1 14.1 20000______________________________________
It can be seen from Table 15 that Nb in the Fe--Nb--B--Cu alloy system can be replaced by Ta and/or Ti, e.g., that Nb can be replaced by Nb and Ti, Ta and Ti or Nb, Ta and Ti.
As will be understood from the above description, the soft magnetic alloy having any of compositions 9 through 16 exhibits a high permeability of 10000 or above, saturation magnetization of 12 to 15.3 kG, excellent heat resistance and a high hardness.
Thus, the above-described soft magnetic alloy is suitable for use as a magnetic core for a noise filter, a magnetic head, a transformer or chalk coil. The use of the above soft magnetic alloy improves performance and reduces the size and weight of such components.
EXAMPLE 16
Regarding the effect of the heat treatment on the magnetic characteristics and structure of the alloy having any of compositions 5 through 8, those of the Fe.sub.84 Nb.sub.7 B.sub.9 alloy, one of the basic compositions 5 through 8, will be described below. The crystallization initiation temperature of the above alloy, obtained by the differential thermal analysis at a heating rate of 10.degree. C./min, was 490.degree. C.
FIG. 28 is a graphic illustration showing the effect of annealing (retained for an hour at each temperature) on the effective permeability (.mu.e) and saturation magnetization (Bs) of the above alloy.
It is clear from FIG. 28 that the effective permeability of the alloy according to the present invention, which is low in a quenched state (RQ) of the alloy, rapidly increases due to the annealing at a temperature ranging from 550.degree. to 680.degree. C. We investigated frequency dependency of the permeability of an approximately 20 .mu.m-thick sample which was subjected to the heat treatment at 650.degree. C., and found the sample exhibited excellent soft magnetic characteristics at high frequencies, like 22000 at 1 kHz, 19000 at 10 kHz and 8000 at 100 kHz. It thus became clear that the magnetic characteristics of the alloy according to the present invention can be adjusted by adequately selecting the heat treating conditions, such as the temperature increasing rate, and improved by annealing in a magnetic field.
In the soft magnetic alloy employed in the present invention, the heat treating temperature should be adequately selected according to the composition thereof in a range from 400.degree. to 750.degree. C.
FIG. 29 shows the results of the measurements regarding an influence of the proportion of B on the effective permeability of the Fe.sub.93-x Nb.sub.7 B.sub.x alloy. In FIG. 29, we examined how permeability changed when the proportion of B was varied between 6 and 10 atomic percent.
It is clear from FIG. 29 that when the proportion of B is between 6.5 and 10 atomic percent, excellent permeability can be obtained. Thus, the present inventors limited the proportion of B to 6.5 to 10 atomic percent in the alloy having either of composition examples 5 through 8.
We investigated changes in the structure of the Fe.sub.93-x Nb.sub.7 B.sub.x alloy, caused by the heat treatment, by the X-ray diffraction method. Also, we observed the structure of the heat treated alloy using a transmission type electronic microscope. The results are shown in FIGS. 30 and 31, respectively.
As shown in FIG. 30, the haloed diffraction pattern characteristic to the amorphous phase is observed in a quenched state, while the diffraction pattern inherent in the crystalline structure is observed after heat treatment. It is thus clear that the structure of the alloy according to the present invention changed from the amorphous phase to the crystalline structure as a consequence of the heat treatment.
It is also clear from FIG. 31 that the heat treated structure is composed of fine grains having a grain size of about 100 to 200 .ANG. (10 to 20 nm).
We examined changes in the hardness of the Fe.sub.84 Nb.sub.7 B.sub.9 alloy, caused by the heat treatment, and found that the hardness increased from 650 DPN, Vickers hardness obtained in a quenched state, to 950 DPN, after the heat treatment.
In the alloy according to the present invention having any of the compositions 5 through 8, the structure mainly composed of super fine grains, obtained by heat treating and thereby crystallizing the amorphous alloy having any of the aforementioned compositions, exhibits high saturation magnetization, excellent soft magnetic characteristics, a high hardness and high thermal stability. Further, since the major elements employed in the alloy according to the present invention do not tend to readily generate an oxide and are thus not readily oxidized during manufacture, manufacture of the alloy is facilitated.
We measured changes in the saturation magnetization of the soft magnetic alloy according to the present invention described in compositions 5 through 8, caused by changes in the proportions of Fe, that of B and that of Nb. The results of the measurements are shown in FIG. 32.
It is clear from FIG. 32 that excellent saturation magnetization of 13 kG to 15 kG can be obtained in the alloy composition range according to the present invention.
The reasons for the limitation of the proportion of Co and that of Ni in the alloy described in compositions 7 and 8 will be described below.
FIG. 33 shows the relation between the proportion of Co and that of Ni (1) in the alloy having a composition expressed by (Fe.sub.1-a Z.sub.a).sub.84 Nb.sub.7 B.sub.9 (Z=Co, Ni) and permeability.
It is apparent from the results shown in FIG. 33 that excellent effective permeability of 5000 or above, which is the same as that of the Fe based amorphous alloy, can be obtained when the proportion of Co and the proportion of Ni are 0.1 or above. When a is more than 0.1 atomic percent, the permeability of the alloy rapidly reduces. Therefore, the present inventors limited the proportion of Co and the proportion of Ni in the alloy employed in the present invention to 0.1 or below.
An alloy, such as a Fe--Nb--Ta--B--Cu alloy system, a Fe--Nb--Ti--B alloy system or a Fe--Nb--Ta--Ti--B alloy system, obtained by replacing Nb in the Fe--Nb--B alloy system by a plurality of elements, will be described. Table 16 shows the results of the measurements conducted to examine the magnetic characteristics of the soft magnetic alloy obtained by heat treating the above alloy at a heating rate of 80.degree. to 100.degree. C./min.
TABLE 16______________________________________Alloy composition Permeability Saturation magnetic(atm %) .mu.e (1 kHz) flux density Bs (kG)______________________________________Fe.sub.84 Nb.sub.7 B.sub.9 23500 15.3Fe.sub.84 Nb.sub.4 Ta.sub.2 Ti.sub.1 B.sub.9 12000 15.0Fe.sub.84 Nb.sub.6 Ti.sub.1 B.sub.9 12500 15.0Fe.sub.84 Nb.sub.6 Ta.sub.1 B.sub.9 11000 14.9______________________________________
It is clear from the results shown in FIG. 16 that similar permeability and saturation magnetization are obtained in the alloys.
It can be seen from Table 16 that Nb in the Fe--Nb--B alloy system can be partially replaced by Ta and/or Ti, e.g., that Nb can be replaced by Nb and Ti, Nb and Ti or Nb, Ta and Ti.
As will be understood from the above description, the soft magnetic alloy having any of compositions 5 through 9 exhibits high permeability, which is equal to or greater than that of the Fe based amorphous alloy, saturation magnetization of about 15 kG, excellent heat resistance and a high hardness.
Thus, the above-described soft magnetic alloy having any of the compositions 5 through 8 is suitable for use as a magnetic core for a noise filter. The use of the soft magnetic alloy as a magnetic core improves performance of the noise filter and reduces size and weight thereof.
EXAMPLE 17
FIG. 34 shows the results of measurements conducted to study how changes in the proportion of Co in an alloy sample having a composition expressed by (Fe.sub.1-x Co.sub.x).sub.90 Zr.sub.7 B.sub.3 affect permeability (.mu.e), magnetostriction (.lambda.s) and saturation magnetization (Bs). The measurements were conducted under the same conditions as those of the measurements conducted in the previous examples.
It can be seen from the results shown in FIG. 34 that permeability of 20000 or above can be obtained when the proportion of Co (a) is between 0.005 and 0.03. Saturation magnetization remains at a high value from 16.4 kG to 17 kG when the proportion of Co is changed.
Magnetostriction varies in a range between -1.times.10.sup.-8 and +3.times.10.sup.-6 according to changes in the proportion of Co. It is therefore apparent that magnetostriction can be adjusted by selecting an adequate composition which is achieved by replacing part of the Fe with Co. Thus, magnetostriction adjustment can take into consideration the influence that the pressure applied during resin molding has on magnetostriction.
EXAMPLE 18
FIG. 35 shows measurements of core loss in a Fe.sub.9 Hf.sub.7 B.sub.4 alloy according to the present invention and in a Fe--Si--B amorphous alloy of a comparative example. Core loss was measured by supplying a sinosoidal current to a wire coiled on a ring-shaped sample in the sin B mode in which Fourier transform is conducted on the measured value.
It is apparent from the results shown in FIG. 35 that the alloy according to the present invention has a core loss less than that of the amorphous alloy of the comparative example at all frequencies including 50 Hz, 400 Hz, 1 kHz, 10 kHz and 50 kHz.
EXAMPLE 19
We manufactured various alloy samples according to the present invention, and examined the relation between the temperature increasing rates during manufacture of such samples and the permeabilities of the manufactured samples. The results of the measurements are shown in FIGS. 36 through 39.
FIG. 36 is a graph showing the relation between the heating rate employed to manufacture a plurality of samples selected from the samples shown in Table 2 and the permeability thereof. FIG. 37 shows the results of the similar measurements conducted on the samples shown in Table 3. FIG. 38 shows the results of the similar measurements conducted on the samples shown in Table 4. FIG. 39 shows the results of the similar measurements conducted on the samples shown in Table 5.
It is clear from the results shown in FIGS. 36 through 39 that for each of the alloys according to the present invention, increasing the heating rate improves permeability.
EXAMPLE 20
FIG. 40 shows the relation between the average grain size of the samples having compositions shown in Table 17 and the coercive force thereof.
TABLE 17______________________________________Alloy composition Average grain size Coercive force(atm %) (nm) (Oe)______________________________________Fe.sub.84 Nb.sub.7 B.sub.9 10 0.1Fe.sub.86 Zr.sub.7 B.sub.6 Cu.sub.1 10 0.03Fe.sub.89 Hf.sub.7 B.sub.4 15 0.07(Fe.sub.0.99 Co.sub.0.01).sub.90 Zr.sub.7 B.sub.3 15 0.07Fe.sub.91 Zr.sub.7 B.sub.2 18 0.09Fe.sub.86 B.sub.14 28.8 4.0Fe.sub.79 Cr.sub.7 B.sub.14 37.2 15.0Fe.sub.78 V.sub.7 B.sub.14 46.9 13.8Fe.sub.83 W.sub.7 B.sub.10 87.2 14.9______________________________________
It is clear from the results shown in FIG. 40 that a low coercive force can be obtained by making the average grain size 30 nm or below.
Attempts have been made by the present inventors to improve magnetic characteristics by improving the heat treatment process of the alloy and thereby obtaining finer grains. According to the theory of crystallization of amorphous alloys (theory of nucleation and growth), fine grains are obtained when the nucleation speed is high and the nucleus growing speed is low. Normally, the nucleation speed and the nucleus growth speed are the function of temperature, and the above-mentioned conditions are accomplished by retaining the alloy at low temperatures for a long time. From this knowledge may be devised a technique of elongating the heat treating time at low temperature regions which is achieved by reducing the heating rate.
However, the present inventors considered increasing the heating rate, which is contrary to the above-described commonly accepted idea, as shown in the following example.
EXAMPLE 21
FIG. 41 shows the relation between the time t it takes for a sample having a composition of Fe.sub.90 Zr.sub.7 B.sub.3 to be crystallized at a fixed temperature of T and the crystallization fraction (crystal volume fraction).
The time t represented by the abscissa axis of FIG. 41 will be explained. It is known that the crystal volume fraction x and the time t have the relation expressed by the following equation, known as JMA (Johnson-Mehl-Avrami).
x=1-exp (-kt.sup.n)
where an exponent n is a variable which differs according to the crystal precipitating mechanism.
The logarithms of the crystal fractions shown in FIG. 41 are plotted in FIG. 42 on the basis of the above-described relation. Obtaining the relation shown in FIG. 42 is called JMA plotting. In FIG. 42, an increase in n means that the number of crystal grains has increased and the orientation of the nuclei has become three-dimensional. According to the normally employed crystal growth mechanism for amorphous substances, the grain size is increased by increasing the heating rate.
It is known that n is from 1.5 to 3 when spherical precipitate is uniformly produced. When the alloy is crystallized at 490.degree. C. or above in FIG. 42, n becomes 1.9 to 2.2, which means that a substantially uniform bbc phase has precipitated. When the alloy is crystallized at a low temperature of 450.degree. C., n becomes 1.0, which implies that the precipitated bcc phase is non-uniform. It is thus clear from the results shown in FIG. 42 that in order to obtain uniform fine grains, crystallization at a higher temperature is effective. Since the crystallization temperature of the amorphous alloy is usually raised in proportion to the heating rate, uniform fine structure is expected from raising the heating rate.
FIG. 43 shows the measurement results of the grain size of the Fe.sub.90 Zr.sub.7 B.sub.3 alloy sample according to the present invention obtained at a heating rate .alpha.=200 .degree. C./min.
FIG. 44 shows the measurement results of the grain size of the alloy sample having the same composition as that shown in FIG. 43, obtained at a heating rate .alpha.=2.5.degree. C./min, which is lower than that employed in FIG. 43.
As can be seen from the grain size distribution of the bcc phase shown in FIGS. 43 and 44, whereas the sample obtained at a heating rate of 200.degree. C./min has a small average grain size and a grain size distribution is sharp and concentrated on a small grain size range, the sample treated at a heating rate of 2.5.degree. C./min has a large average grain size and a broad grain size distribution.
As will be understood from the foregoing description, it is apparent that in the alloy according to the present invention, a small average grain size is obtained by increasing the heating rate, which is contrary to a commonly accepted idea.
EXAMPLE 22
FIGS. 45 and 46 show the structures of the Fe.sub.90 Zr.sub.7 B.sub.3 amorphous alloys obtained using a transmission type electronic microscope to examine the grain size of the alloy structure.
In the results shown in FIGS. 45 and 46, only special crystals are shown, because the structure was observed in a dark-field image. However, the entire structure is composed of the similar crystals.
It is apparent from the results shown in FIGS. 45 and 46 that the alloy structure obtained at a higher heating rate has finer grains than that of the alloy structure obtained at a lower heating rate.
EXAMPLE 23
The present inventors manufactured the samples having compositions shown in Table 18 and conducted corrosion resistance test on them under the conditions of 40.degree. to 60.degree. C. and 96% RH for 96 hours. In Table 18, the samples which did not corrode are indicated by o, those which corroded at 1% of the entire area or less are indicated by .DELTA., and those which corroded at 1% of the entire area or more are indicated by x.
TABLE 18______________________________________Alloy composition (atm %) Permeability .mu. Corroded state______________________________________Fe.sub.89 Zr.sub.7 B.sub.3 Ru.sub.1 19800 .DELTA.Fe.sub.82.5 Zr.sub.4 Nb.sub.3 B.sub.6.5 Cu.sub.1 Ru.sub.3 24000 .smallcircle.Fe.sub.84.5 Zr.sub.7 B.sub.5 Cu.sub.1 Cr.sub.0.5 Ru.sub.2 28000 .smallcircle.Fe.sub.85 Zr.sub.3.5 Nb.sub.3.5 B.sub.7 Cu.sub.1 32000 x(Comparative example)Fe.sub.80 Zr.sub.7 B.sub.6 Cu.sub.1 Cr.sub.8 800 .smallcircle.(Comparative example)______________________________________
As can be seen from Table 18, the samples according to the present invention exhibited excellent corrosion resistance. It became clear from the results of the test that the addition of 5 atomic percentage or below of Ru and Cr improves corrosion resistance of the alloy according to the present invention without deteriorating the magnetic characteristics.
EXAMPLE 24
Regarding the amorphous alloy samples having compositions shown in Table 20, the measurement results of core loss, magnetostriction (.lambda.s) and specific electric resistance (.rho.) are shown in Table 20. The thickness (t) of each of the samples is also shown in Table 20. Measurements were conducted on the samples according to the present invention at a heating rate of 80.degree. to 100.degree. C./min and at a heat treating temperature of 650.degree. C. The temperature at which heat treatment was conducted on Fe--Si--B amorphous alloy was 370.degree. C.
TABLE 19______________________________________ Fe--Si--B Amorphous Fe.sub.90 Zr.sub.7 B.sub.3 Fe.sub.89 Hf.sub.7 B.sub.4 Fe.sub.84 Nb.sub.7 B.sub.9 alloyStructure bcc bcc bcc Amorphous______________________________________.sup.w 14/50.sup.a 0.21 0.14 0.19 0.24(w/kg).sup.w 10/400.sup.a 0.82 0.61 0.97 1.22(w/kg).sup.w 10/1 k.sup.a 2.27 1.70 2.50 3.72(w/kg).sup.w 2/100 k.sup.a 79.7 59.0 75.7 1.68(w/kg).sup..lambda. s .times. 10.sup.6 -1..sub.1 -1..sub.2 0..sub.1 27p .times. 10.sup.8 (.OMEGA.m) 44 48 58 137t (.mu.m) 18 17 22 20______________________________________ .sup.a w.sub..alpha./.beta. : Core loss (.alpha. .times. 10.sup.-1 T and .beta. Hz) .sup.b f = 1 kHz, Hm = 5 mOe
It is clear from Table 19 that the core loss, magnetostriction and specific resistance of the alloy samples according to the present invention are all lower than those of the Fe--Si--B amorphous alloy of Comparative Example.
EXAMPLE 25
A core element 19 shown in FIG. 1 was manufactured using the alloy having a composition expressed by Fe.sub.84 Nb.sub.7 B.sub.9, and the manufactured core element 19 was incorporated in an electrical circuit 20 to manufacture a noise filter 22 shown in FIG. 47.
The pulse damping characteristics of the noise filter 22 was measured.
To manufacture the magnetic core, a ribbon was manufactured by the single roll method using the alloy having a composition expressed by Fe.sub.84 Nb.sub.7 B.sub.9, the obtained ribbon was coiled in a toroidal fashion into a ring-like form, and that toroidal ribbon was heat treated.
The width of the ribbon was 15 mm, and the thickness thereof was 40 .mu.m. The inner diameter of the annular magnetic core was 10 mm, and the outer diameter thereof was 20 mm.
To measure the pulse attenuation characteristics, the noise filter 22 according to the present invention was
It is clear from Table 19 that the core loss, magnetostriction and specific resistance of the amorphous alloy samples according to the present invention are all lower than those of the Fe--Si--B amorphous alloy of Comparative Example.
EXAMPLE 25
A core element 19 shown in FIG. 1 was manufactured using the alloy having a composition expressed by Fe.sub.84 Nb.sub.7 B.sub.9, and the manufactured core element 19 was incorporated in an electronic circuit 20 to manufacture a noise filter 22 shown in FIG. 47.
The pulse damping characteristics of the noise filter 22 was measured.
To manufacture the magnetic core, a ribbon was manufactured by the single roll method using the alloy having a composition expressed by Fe.sub.84 Nb.sub.7 B.sub.9, the obtained ribbon was coiled in a toroidal fashion into a ring-like form, and that toroidal ribbon was heat treated.
The width of the ribbon was 15 mm, and the thickness thereof was 40 .mu.m. The inner diameter of the annular magnetic core was 10 mm, and the outer diameter thereof was 20 mm.
To measure the pulse attenuation characteristics, the noise filter 22 according to the present invention was incorporated in a circuit shown in FIG. 48 including a noise simulator 26, and the output voltage of the circuit was measured each time an input voltage having a pulse width of 800 nS was varied by 0.1 KV from 0.1 KV to 2.0 KV.
Measurements were also conducted on Comparative Examples including a conventional magnetic core employing a ferrite and a core employing a Fe-based amorphous alloy.
FIG. 49 shows the results of the measurements. In FIG. 49, the pulse attenuation characteristics of the noise filter employing Fe.sub.84 Nb.sub.7 B.sub.9 are shown by -.diamond.-, those of ferrite are shown by -.quadrature.-, and those of the Fe-based amorphous alloy are shown by -+-.
As can be seen from FIG. 49, whereas the output voltage of the noise filter employing ferrite rapidly increases when the input voltage is about 0.7 KV, that of the noise filter employing Fe.sub.84 Nb.sub.7 B.sub.9 remains at 40 V when the input voltage is 2.0 KV. Thus, the noise filter according to the present invention exhibits excellent attenuation characteristics.
The noise filter employing the Fe-based amorphous alloy exhibits better damping characteristics than those of the noise filter employing ferrite but inferior damping characteristics to those of the noise filter according to the present invention.
The noise filter according to the present invention exhibits excellent pulse damping characteristics particularly when the input voltage is high.
EXAMPLE 26
Regarding three types of noise filters manufactured in Example 25, the damping characteristics (static characteristics) in both normal mode and common mode were measured.
The measurements in the normal mode are those of the attenuation characteristics of the noise filter incorporated in the circuit shown in FIG. 50 relative to the wavelength, and the measurements in the common mode are those of the damping characteristics of the noise filter incorporated in the circuit shown in FIG. 51 relative to the wavelength. In FIGS. 50 and 51, reference numeral 28 denotes a tracking generator. Reference numeral 30 denotes a spectrum analyzer. Reference numerals 31 and 32 respectively denote a balance unbalance transformer which transforms unbalance to balance and a balance-unbalance transformer which transforms balance to unbalance.
FIG. 52 shows the results of the measurements. In FIG. 52, the attenuation characteristics of the noise filter employing Fe.sub.84 Nb.sub.7 B.sub.9 in the normal mode are indicated by -.gradient.-, those of the noise filter employing ferrite in the normal mode are indicated by -.DELTA.-, and those of the noise filter employing the Fe-based amorphous alloy in the normal mode are indicated by -.times.-. The attenuation characteristics of the noise filter employing Fe.sub.84 Nb.sub.7 B.sub.9 in the common mode are indicated by -.diamond.-, those of the noise filter employing ferrite in the common mode are indicated by -.quadrature.-, and those of the noise filter employing the Fe-based amorphous alloy in the common mode are indicated by -+-.
As can be seen from FIG. 52, in the normal mode, whereas the noise filter employing ferrite exhibits excellent attenuation characteristics when the frequency is 1 MHz or below, the noise filter employing Fe.sub.84 Nb.sub.7 B.sub.9 exhibits excellent attenuation characteristics when the frequency is 1 MHz or above.
In the common mode, the noise filter according to the present invention exhibits similar attenuation characteristics to those of the noise filter employing ferrite when the frequency is 1 MHz or below. When the frequency is 3 MHz or above, the attenuation characteristics of the noise filter according to the present invention are far better than those of the noise filter employing ferrite.
Thus, the noise filter according to the present greatly attenuates high frequency noise.
Generally, a magnetic core of a noise filter for the common mode operation requires a magnetic material having a high permeability, and a magnetic core for a noise filter for the normal mode operation requires high permeability and high saturation magnetization. In the present invention, since the soft magnetic alloy used as the magnetic core exhibits high permeability and high saturation magnetization, the noise filter according to the present invention can thus be applied for both common and normal modes.
As will be understood from the foregoing description, since the noise filter according to the present invention employs, as a magnetic core thereof, a Fe-based soft magnetic alloy exhibiting soft magnetic characteristics as excellent as those of a conventional alloy and exhibiting high permeability and high saturation magnetization, the noise filter exhibits excellent attenuation characteristics and enables the size thereof to be reduced.
Particularly, the noise filter according to the present invention exhibits excellent pulse attenuation characteristics at high input voltages, and excellent damping characteristics at high frequencies.
In the soft magnetic alloy employed in the present invention, permeability can be stably enhanced by performing heat treatment at a heating rate of 1.0.degree. C./min or above.
In the alloy employed in the magnetic core, since both Nb and Ta to be added to the alloy are thermally stable, changes in the properties thereof due to oxidation or reduction during manufacture are less. This is advantageous for manufacture of the magnetic core.

Claims

1. A noise filter comprising:
an annular magnetic core made of a soft magnetic alloy ribbon consisting of Fe, B and at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo, W, Cr, Ru, Rh, Ir, Co and Ni, wherein at least 50% of said soft magnetic alloy ribbon is composed of fine grains of body-centered cubic structure having an average grain size of 30 nm or below;
a casing for accommodating said magnetic core;
a pair of coils separated from each other; and
an electrical circuit connecting to a core element made up of said magnetic core, said casing and said coils.
2. A noise filter according to claim 1, wherein an insulating material fixes said magnetic core to said casing.
3. A noise filter according to claim 1, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
Fe.sub.b B.sub.M.sub.y
where M is at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W combined with Zr and/or Hf, and b, x and y are atomic percentages which respectively satisfy 75<b<93, 0.5<x<10, and 4<y<9.
4. A noise filter according to claim 1, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
Fe.sub.b B.sub.x M.sub.y X.sub.u
where M is at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W combined with Zr and/or Hf, X is at least one element selected from a group consisting of Cr, Ru, Rh and Ir, and b, x, y and u are atomic percentages which respectively satisfy 75<b<93, 0.5<x<10, 4<y<9, and u.ltoreq.5.
5. A noise filter according to claim 1, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
(Fe.sub.1-a Z.sub.a).sub.b B.sub.x M.sub.y
where Z is Co and/or Ni, M is at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W combined with Zr and/or Hf, and a, b, x and y are atomic percentages which respectively satisfy a<0.1, 75<b<93, 0.5<x<10, and 4<y<9.
6. A noise filter according to claim 1, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
(Fe.sub.1-a Z.sub.a).sub.b B.sub.x M.sub.y X.sub.u
where Z is Co and/or Ni, M is at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W combined with Zr and/or Hf, X is at least one element selected from a group consisting of Cr, Ru, Rh and Ir, and a, b, x and y are atomic percentages which respectively satisfy a<0.1, 75<b93, 0.5<x<10, 4<y<9, and u<5.
7. A noise filter according to claim 1, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
Fe.sub.b B.sub.x M'.sub.y
where M' is at least one element selected from a group consisting of Ti, V, Nb, Ta, Mo and W combined with Nb, and b, x and y are atomic percentages which respectively satisfy 75<b<93, 6.5<x<10, and 4<y<9.
8. A noise filter according to claim 1, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
Fe.sub.b B.sub.x M'.sub.y X.sub.u
where M' is at least one element selected from a group consisting of Ti, V, Nb, Ta, Mo and W combined with Nb, X is at least one element selected from a group consisting of Cr, Ru, Rh and Ir, and b, x, y and u are atomic percentages which respectively satisfy 75<b<93, 6.5<x<10, 4<y<9, and u<5.
9. A noise filter according to claim 1, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
(Fe.sub.1-a Z.sub.a).sub.b B.sub.x M'.sub.y
where Z is Co and/or Ni, M' is at least one element selected from a group consisting of Ti, V, Nb, Ta, Mo and W combined with Nb, and a, b, x and y are atomic percentages which respectively satisfy a<0.1, 75<b<93, 6.5<x<10, and 4<y<9.
10. A noise filter according to claim 1, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
(Fe.sub.1-a Z.sub.a).sub.b B.sub.x M'.sub.y X.sub.u
where Z is Co and/or Ni, M' is at least one element selected from a group consisting of Ti, V, Nb, Ta, Mo and W combined with Nb, X is at least one element selected from a group consisting of Cr, Ru, Rh and Ir, and a, b, x, y and u are atomic percentages which respectively satisfy a<0.1, 75<b<93, 6.5<x<10, 4<y<9, and u<5.
11. A noise filter comprising:
an annular magnetic core made of a soft magnetic alloy ribbon consisting of Fe, B, and at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo, W, Cr, Ru, Rh, Ir, Co, Ni, Cu, Ag, Au, Pd, Pt and Bi, wherein at least 50% of said soft magnetic alloy ribbon is composed of fine grains of body-centered cubic structure having an average grain size of 30 nm or below, and wherein the soft magnetic alloy ribbon is wound in a plurality of layers such that surfaces of adjacent layers are in direct contact;
a casing for accommodating said magnetic core;
a pair of coils separated from each other; and
an electrical circuit connecting to a core element made up of said magnetic core, said casing and said coils.
12. A noise filter according to claim 11, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
Fe.sub.b B.sub.x M.sub.y T.sub.z
where M is at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W combined with Zr and/or Hf, T is at least one element selected from a group consisting of Cu, Ag, Au, Pd, Pt and Bi, and b, x, y and z are atomic percentages which respectively satisfy 75<b<93, 0.5<x18, 4<y<10, and z<4.5.
13. A noise filter according to claim 12, wherein 0.2<z<4.5.
14. A noise filter according to claim 11, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
ti Fe.sub.b B.sub.x M.sub.y T=X.sub.u
where M is at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W combined with Zr and/or Hf, T is at least one element selected from a group consisting of Cu, Ag, Au, Pd, Pt and Bi, X is at least one element selected from a group consisting of Cr, Ru, Rh and Ir, and b, x, y, z and u are atomic percentages which respectively satisfy 75<b<93, 0.5<x18, 4<y<10, z<4.5, and u<5.
15. A noise filter according to claim 14, wherein 0.2<z<4.5.
16. A noise filter according to claim 11, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
(Fe.sub.1-a Z.sub.a).sub.b B.sub.x M.sub.y T.sub.z
where Z is Co and/or Ni, M is at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W combined with Zr and/or Hf, T is at least one element selected from a group consisting of Cu, Ag, Au, Pd, Pt and Bi, and a, b, x, y and z are atomic percentages which respectively satisfy a<0.1, 75<b<93, 0.5<x<18, 4<y<10, and z<4.5.
17. A noise filter according to claim 16, wherein 0.2<z<4.5.
18. A noise filter according to claim 11, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
(Fe.sub.1-a Z.sub.a).sub.b B.sub.x M.sub.y T.sub.z X.sub.u
where Z is Co and/or Ni, M is at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W combined with Zr and/or Hf, T is at least one element selected from a group consisting of Cu, Ag, Au, Pd, Pt and Bi, X is at least one element selected from a group consisting of Cr, Ru, Rh and Ir, and a, b, x, y, z and u are atomic percentages which respectively satisfy a<0.1, 75<b<93, 0.5<x<18, 4<y<10, z<4.5 and u<5.
19. A noise filter according to claim 18, wherein 0.2<z<4.5.
20. A noise filter according to claim 11, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
Fe.sub.b B.sub.x M'.sub.y T.sub.z
where M' is at least one element selected from a group consisting of Ti, V, Nb, Ta, Mo and W combined with any of Ti, Nb and Ta, T is at least one element selected from a group consisting of Cu, Ag, Au, Pd, Pt and Bi, and b, x, y and z are atomic percentages which respectively satisfy 75<b<93, 6.5<x<18, 4<y<10, and z<4.5.
21. A noise filter according to claim 20, wherein 0.2<z<4.5.
22. A noise filter according to claim 11, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
Fe.sub.b B.sub.x M'.sub.y T.sub.z X.sub.u
where M' is at least one element selected from a group consisting of Ti, V, Nb, Ta, Mo and W combine with any of Ti, Nb and Ta, T is at least one element selected from a group consisting of Cu, Ag, Au, Pd, Pt and Bi, X is at least one element selected from a group consisting of Cr, Ru, Rh and Ir, and b, x, y, z and u are atomic percentages which respectively satisfy 75<b<93, 6.5<x<18, 4<y<10, z<4.5, and u<5.
23. A noise filter according to claim 22, wherein 0.2<z<4.5.
24. A noise filter according to claim 11, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
(Fe.sub.1-a Z.sub.a).sub.b B.sub.x M'.sub.y T.sub.z
where Z is Co and/or Ni, M' is at least one element selected from a group consisting of Ti, V, Nb, Ta, Mo and W combined with any of Ti, Nb and Ta, T is at least one element selected from a group consisting of Cu, Ag, Au, Pd, Pt and Bi, and a, b, x, y and z are atomic percentages which respectively satisfy a<0.1, 75<b<93, 6.5<x<18, 4<y<10, and z<4.5.
25. A noise filter according to claim 24, wherein 0.2<z<4.5.
26. A noise filter according to claim 11, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
(Fe.sub.1-a Z.sub.a).sub.b B.sub.x M'.sub.y T.sub.z X.sub.u
where Z is Co and/or Ni, M' is at least one element selected from a group consisting of Ti, V, Nb, Ta, Mo and W combined with any of Ti, Nb and Ta, T is at least one element selected from a group consisting of Cu, Ag, Au, Pd, Pt and Bi, X is at least one element selected from a group consisting of Cr, Ru, Rh and Ir, and a, b, x, y, z and u are atomic percentages which respectively satisfy a<0.1, 75<b<93, 6.5<x18, 4<y<10, z<4.5, and u<5.
27. A noise filter according to claim 26, wherein 0.2<z<4.5.
28. A magnetic core comprising a soft magnetic alloy ribbon consisting of Fe, B and at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo, W, Cr, Ru, Rh, Ir, Co and Ni, wherein at least 50% of said soft magnetic alloy ribbon is composed of fine grains of body-centered cubic structure having an average grain size of 30 nm or below.
29. The magnetic core of claim 28, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
Fe.sub.b B.sub.x M.sub.y X.sub.u
where M is at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W combined with Zr and/or Hf, X is at least one element selected from a group consisting of Cr, Ru, Rh and Ir, and b, x, y and u are atomic percentages which respectively satisfy 75<b<93, 0.5<x5 10, 4<y<9, and u<5.
30. The magnetic core of claim 28, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
(Fe.sub.1-a Z.sub.a).sub.b B.sub.x M.sub.y
where Z is Co and/or Ni, M is at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W combined with Zr and/or Hf, and a, b, x and y are atomic percentages which respectively satisfy a<0.1, 75<b<93, 0.5<x<10, and 4<y<9.
31. The magnetic core of claim 28, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
(Fe.sub.1-a Z.sub.a).sub.b B.sub.x M.sub.y X.sub.u
where Z is Co and/or Ni, M is at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W combined with Zr and/or Hf, X is at least one element selected from a group consisting of Cr, Ru, Rh and Ir, and a, b, x and y are atomic percentages which respectively satisfy a<0.1, 75<b<93, 0.5<x<10, 4<y<9, and u<5.
32. The magnetic core of claim 28, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
Fe.sub.b B.sub.x M'.sub.y
where M' is at least one element selected from a group consisting of Ti, V, Nb, Ta, Mo and W combined with Nb, and b, x and y are atomic percentages which respectively satisfy 75<b<93, 6.5<x<10, and 4<y<9.
33. The magnetic core of claim 28, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
Fe.sub.b B.sub.x M'.sub.y X.sub.u
where M' is at least one element selected from a group consisting of Ti, V, Nb, Ta, Mo and W combined with Nb, X is at least one element selected from a group consisting of Cr, Ru, Rh and Ir, and b, x, y and u are atomic percentages which respectively satisfy 75<b<93, 6.5<x<10, 4<y<9, and u<5.
34. The magnetic core of claim 28, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
(Fe.sub.1-a Z.sub.a).sub.b B.sub.x M'.sub.y
where Z is Co and/or Ni, M' is at least one element selected from a group consisting of Ti, V, Nb, Ta, Mo and W combined with Nb, and a, b, x and y are atomic percentages which respectively satisfy a<0.1, 75<b93, 6.5<x10, and 4<9.
35. The magnetic core of claim 28, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
(Fe.sub.1-a Z.sub.a).sub.b B.sub.x M'.sub.y X.sub.u
where Z is Co and/or Ni, M' is at least one element selected from a group consisting of Ti, V, Nb, Ta, Mo and W combined with Nb, X is at least one element selected from a group consisting of Cr, Ru, Rh and Ir, and a, b, x, y and u are atomic percentages which respectively satisfy a<0.1, 75<b93, 6.5<x10, 4<y<9, and u<5.
36. The magnetic core of claim 28, wherein said soft magnetic alloy ribbon has a composition expressed by the general formula:
Feb B.sub.x M.sub.y
where M is at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W combined with Zr and/or Hf, and b, x and y are atomic percentages which respectively satisfy 75<b<93, 0.5<x<10, and 4<y<9.
37. A magnetic core comprising a soft magnetic alloy ribbon consisting of Fe, B, and at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo, W, Cr, Ru, Rh, Ir, Co, Ni, Cu, Ag, Au, Pd, Pt and Bi, wherein at least 50% of said soft magnetic alloy ribbon is composed of fine grains of body-centered cubic structure having an average grain size of 30 nm or below, and wherein the soft magnetic alloy ribbon is wound in a plurality of layers such that surfaces of adjacent layers are in direct contact.
38. The magnetic core of claim 37, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
Fe.sub.b B.sub.x M.sub.y T.sub.z X.sub.u
where M is at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W combined with Zr and/or Hf, T is at least one element selected from a group consisting of Cu, Ag, Au, Pd, Pt and Bi, X is at least one element selected from a group consisting of Cr, Ru, Rh and Ir, and b, x, y, z and u are atomic percentages which respectively satisfy 75<b<93, 0.5<x<18, 4<y<10, z<4.5, and u<5.
39. The magnetic core of claim 38, wherein 0.2<z<4.5.
40. The magnetic core of claim 37, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
(Fe.sub.1-a Z.sub.a).sub.b B.sub.x M.sub.y T.sub.z
where Z is Co and/or Ni, M is at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W combined with Zr and/or Hf, T is at least one element selected from a group consisting of Cu, Ag, Au, Pd, Pt and Bi, and a, b, x, y and z are atomic percentages which respectively satisfy a<0.1, 75<b<93, 0.5<x18, 4<y<10, and z4.5.
41. The magnetic core of claim 40, wherein 0.2<z<4.5.
42. The magnetic core of claim 37, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
(Fe.sub.1-a Z.sub.a).sub.b B.sub.x M.sub.y T.sub.z X.sub.u
where Z is Co and/or Ni, M is at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W combined with Zr and/or Hf, T is at least one element selected from a group consisting of Cu, Ag, Au, Pd, Pt and Bi, X is at least one element selected from a group consisting of Cr, Ru, Rh and Ir, and a, b, x, y, z and u are atomic percentages which respectively satisfy a<0.1, 75<b<93, 0.5<x18, 4<y<10, z<4.5 and u<5.
43. The magnetic core of claim 42, wherein 0.2<z<4.5.
44. The magnetic core of claim 37, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
Fe.sub.b B.sub.x M'.sub.y T.sub.z
where M' is at least one element selected from a group consisting of Ti, V, Nb, Ta, Mo and W combined with any of Ti, Nb and Ta, T is at least one element selected from a group consisting of Cu, Ag, Au, Pd, Pt and Bi, and b, x, y and z are atomic percentages which respectively satisfy 75<b<93, 6.5<x18, 4<y<10, and z<4.5.
45. The magnetic core of claim 44, wherein 0.2<z<4.5.
46. The magnetic core of claim 37, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
Fe.sub.b B.sub.x M'.sub.y T.sub.z X.sub.u
where M' is at least one element selected from a group consisting of Ti, V, Nb, Ta, Mo and W combine with any of Ti, Nb and Ta, T is at least one element selected from a group consisting of Cu, Ag, Au, Pd, Pt and Bi, X is at least one element selected from a group consisting of Cr, Ru, Rh and Ir, and b, x, y, z and u are atomic percentages which respectively satisfy 75<b<93, 6.5<x18, 4<y<10, z<4.5, and u<5.
47. The magnetic core of claim 46, wherein 0.2<z<4.5.
48. The magnetic core of claim 37, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
(Fe.sub.1-a Z.sub.a).sub.b B.sub.x M'.sub.y T.sub.z
where Z is Co and/or Ni, M' is at least one element selected from a group consisting of Ti, V, Nb, Ta, Mo and W combined with any of Ti, Nb and Ta, T is at least one element selected from a group consisting of Cu, Ag, Au, Pd, Pt and Bi, and a, b, x, y and z are atomic percentages which respectively satisfy a<0.1, 75<b<93, 6.5<x18, 4<y10, and z<4.5.
49. The magnetic core of claim 48, wherein 0.2<z<4.5.
50. The magnetic core of claim 37, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
(Fe.sub.1-a Z.sub.a).sub.b B.sub.x M'.sub.y T.sub.z X.sub.u
where Z is Co and/or Ni, M' is at least one element selected from a group consisting of Ti, V, Nb, Ta, Mo and W combined with any of Ti, Nb and Ta, T is at least one element selected from a group consisting of Cu, Ag, Au, Pd, Pt and Bi, X is at least one element selected from a group consisting of Cr, Ru, Rh and Ir, and a, b, x, y, z and u are atomic percentages which respectively satisfy a<0.1, 75<b<93, 6.5<x<18, 4<y<10, z<4.5, and u<5.
51. The magnetic core of claim 50, wherein 0.2<z<4.5.
52. The magnetic core of claim 37, wherein said soft magnetic alloy ribbon has a composition expressed by the following general formula:
Fe.sub.b B.sub.x M.sub.y T.sub.z
where M is at least one element selected from a group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W combined with Zr and/or Hf, T is at least one element selected from a group consisting of Cu, Ag, Au, Pd, Pt and Bi, and b, x, y and z are atomic percentages which respectively satisfy 75<b<93, 0.5<x<18, 4<y<10, and z<4.5.
53. The magnetic core of claim 52, wherein 0.2<z<4.5.

Priority Claims (1)

Number	Date	Country	Kind
5-190673	Jul 1993	JPX

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Noise filter comprising a soft magnetic alloy ribbon core

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