Title of Invention

FERRITE MAGNET AND METHOD OF PRODUCING SAME

Abstract A ferrite magnet having a basic composition represented by the following general formula: (A1-xRx)O-n[(Fe1-yMy)2O3] by atomic ratio, wherein A is Sr and/or Ba, R is at least one of rare earth elements including Y, M is at least one element selected from the group consisting of Co, Mn, Ni and Zn, and x, y and n are numbers meeting the conditions of 0.01=x=0.4, [x/(2.6n)]=y=[x/(1.6n)], and 5=n=6, and substantially having a magnetoplumbite-type crystal structure, is obtained by uniformly mixing a compound of Sr and/or Ba with an iron compound; calcining the resultant uniform mixture; adding a compound of the R element and/or the M element to the resultant calcined powder at a pulverization step thereof; and sintering the resultant mixture. The compound of the R element and/or the M element may be added at a percentage of more than 0 atomic % and 80 atomic % or less, on an element basis, at a mixing step before calcination.
Full Text The present invention relates to a method for producing an
anisotropic, sintered ferrite magnet.
The present invention relates to a high-performance ferrite magnet
having substantially a magnetoplumbite-type crystal structure extremely
useful for wide ranges of magnet applications such as rotors for
automobiles or electric apparatuses, magnet rolls for photocopiers, etc.,
particularly to a high-performance ferrite magnet having a microstructure
having a higher coercivity iHc (or higher coercivity iHc and residual
magnetic flux density Br) than those of the conventional ferrite magnets
and optionally a high squareness ratio Hk/iHc, and a method for producing
such a high-performance ferrite magnet.
BACKGROUND OF 1HE INVENTION
Ferrite magnets are widely used in various applications including
rotors of motors, electric generators, etc. Recently, ferrite magnets having
higher magnetic properties are required particularly for the purposes of
miniaturization and reduction in weight in the field of rotors for
automobiles and increase in performance in the field of rotors for electric
apparatuses.
High-performance sintered magnets such as Sr ferrite or Ba ferrite
are conventionally produced through the following processes. First, iron
oxide is mixed with a carbonate, etc. of Sr or Ba and then calcined to cause
a ferritization reaction (ferrite-forming reaction). The resultant calcined
clinker is coarsely pulverized, mixed with SiO2, SrCO3, CaCO3, etc. for
controlling sintering behavior and A12O3, Cr2O3, etc. for controlling iHc,
and then finely pulverized to an average diameter of 0.7-1.2 mm in a
solvent. A slurry containing the finely pulverized ferrite-forming material
is wet-molded while being oriented in a magnetic field. The resultant
green body is dried, sintered and then machined to a desired shape. To
increase the properties of the ferrite magnets produced by such a method,
there are the following five methods available.
The first method is a fine pulverization method. When the size of
crystal grains in the sintered body is close to about 0.9 mm, a critical single
magnetic domain diameter of a magnetoplumbite (M)-type Sr ferrite
magnet, its iHc is maximum. Accordingly, fine pulverization may be
carried out to an average diameter of 0.7 mm or less, for instance, taking
into consideration the crystal grain growth at the time of sintering. This
method is, however, disadvantageous in that finer pulverization leads to
poorer water removal at the time of wet molding, resulting in poorer
production efficiency.
The second method is to make the sizes of the crystal grains in the
sintered body as uniform as possible. Ideally, the sizes of the crystal
grains are made as uniformly as possible equal to the above critical single
magnetic domain diameter (about 0.9 mm), because crystal grains larger
than or smaller than this size have low iHc. Specific means for achieving
high performance in this method is to improve a particle size distribution of
fine powder. In commercial production, however, other pulverization
apparatuses than ball mills, attritors, etc. cannot be used, naturally posjng
limitations in the level of improvement in magnetic properties by fine
pulverization. Also, an attempt was recently published to produce fine
ferrite powder having a uniform particle size by a chemical precipitation
method. Such method is, however, not suitable for industrial mass
production.
The third method is to improve crystal orientation affecting
magnetic anisotropy. Specific means in this method is to improve the
dispersion of ferrite particles in a fine powder slurry by adding a surfactant,
or to increase the intensity of a magnetic field at the time of orientation,
etc.
The fourth method is to improve the density of a sintered body. A
Sr ferrite sintered body has a theoretical density of 5.15 g/cc. Sr ferrite
magnets commercially available at present have densities ranging from 4.9
g/cc to 5.0 g/cc, corresponding to 95-97% of the theoretical density.
Though improvement in Br is expected by increasing the density of a
ferrite magnet, a higher density than the above level needs such density-
increasing means as HIP, etc. However, the use of such density-
increasing means leads to increase in the production cost of ferrite magnets,
depriving the ferrite magnets of advantages as inexpensive magnets.
The fifth method is to improve a saturation magnetization as or a
crystal magnetic anisotropy constant of a ferrite compound per se, which is
a main component (main phase) of the ferrite magnet. It is likely that the
improvement in the saturation magnetization as directly leads to
improvement in the residual magnetic flux density Br of the ferrite magnet.
It is also likely that the improvement in the crystal magnetic anisotropy
constant leads to improvement in the coercivity iHc of the ferrite magnet.
Though research is being carried out on W-type ferrite having a higher
saturation magnetization than that of the conventional ferrite compound
having an M-type crystal structure, the W-type ferrite has not been
subjected to mass production because of difficulty in the control of a
sintering atmosphere.
Widely used at present among the above methods for improving the
properties of ferrite magnets are the first to fourth methods, though it is
difficult to drastically improve the properties of ferrite having a main phase
expressed by SrOnFe203 by the first to fourth methods for the reasons
described below. The first reason is that the above first to fourth methods
include conditions lowering productivity or steps difficult to carry out from
the aspect of mass production. The second reason is that further
improvement in magnetic properties, particularly Br, is extremely difficult
because they are close to the theoretically highest level.
Next, as a result of investigation of a hexagonal magnetoplumbite-
type sintered ferrite magnet described in Japanese Patent Laid-Open No. 9-
115715, it has been found that higher iHc cannot easily be achieved.
It may be considered as a specific means for the above fifth method
to mix ferrite expressed by AOnFe203, wherein A is Sr and/or Ba, with
other types of metal compounds such as metal oxides to replace part of A
and Fe elements in the ferrite with other elements thereby improving the
magnetic properties of the ferrite.
The magnetism of the magnetoplumbite-type ferrite magnet is
derived from a magnetic moment of Fe ions, with a magnetic structure of a
ferri-magnet in which magnetic moment is arranged partially in antiparallel
by Fe ion sites. There are two methods to improve the saturation
magnetization in this magnetic structure. The first method is to replace
the Fe ions at sites corresponding to the antiparallel-oriented magnetic
moment with another element, which has a smaller magnetic moment than
Fe ions or is non-magnetic. The second method is to replace the Fe ions
at sites corresponding to the parallel-oriented magnetic moment with
another element having a larger magnetic moment than Fe ions.
Also, increase in a crystal magnetic anisotropy constant in the
above magnetic structure can be achieved by replacing Fe ions with another
element having a stronger interaction with the crystal lattice. Specifically,
Fe ions are replaced with an element in which a magnetic moment derived
from an orbital angular momentum remains or is large.
With the above findings in mind, research has been conducted for
the purpose of replacing Fe ions with various elements by adding various
metal compounds such as metal oxides. As a result, it has been found that
Mn, Co and Ni are elements remarkably improving magnetic properties.
However, the mere addition of the above elements would not provide
ferrite magnets with fully improved magnetic properties, because the
replacement of Fe ions with other elements would destroy the balance of
ion valance, resulting in the generation of undesirable phases. To avoid
this phenomenon, ion sites of Sr and/or Ba should be replaced with other
elements for the purpose of charge compensation. For this purpose, the
addition of La, Nd, Pr, Ce, etc. is effective, resulting in magnetoplumbite-
type ferrite magnets having high Br or high Br and coercivity.
When compounds of rare earth elements such as La and compounds
of M elements such as Co are added to produce high-performance ferrite
magnets by the fifth method, it is usual to carry out the addition of such
compounds before the calcination, namely before the ferritization reaction.
Such addition method is called herein "prior-addition method." Though
the ferrite magnets formed by the prior-addition method have high Br and
high iHc, the squareness ratio Hk/iHc tends to remarkably decrease as the
amounts of these elements added increase, particularly when R is La and M
is Co. The tendency of decrease in the squareness rajjo Hk/iHc by the
prior-addition method is also appreciated in the case of R = La, M = Co +
Zn, or M = Co + JVJn. Because the critical demagnetizing field intensity
decreases by decrease in the squareness ratio Hk/iHc, the ferrite magnets
are likely to lose its magnetization. How easily the ferrite magnets lose
their magnetization is critical particularly when the ferrite magnets are
assembled in magnetic circuits for rotors, etc. Ferrite magnets with higher
squareness ratio Hk/iHc are thus desired.
Therefore, high-performance ferrite magnets satisfactory both in a
coercivity iHc (or coercivity iHc and residual magnetic flux density Br) and
in a squareness ratio Hk/iHc are desired.
Accordingly, an object of the present invention is to provide a high-
performance ferrite magnet having substantially a magnetoplumbite-type
crystal structure, which has higher coercivity iHc (or higher coercivity iHc
and residual magnetic flux density Br) than those of conventional ferrite
magnets and also has high squareness ratio Hk/iHc, thus useful in wide
varieties of magnet applications such as rotors for automobiles and electric
appliances, magnet rolls for photocopiers, etc., and a method for producing
such a high-performance ferrite magnet.
Another object of the present invention is to provide a high-
performance ferrite magnet having substantially a magnetoplumbite-type
crystal structure, which has higher coercivity iHc (or higher coercivity iHc
and residual magnetic flux density Br) and higher squareness ratio Hk/iHc
than those of conventional ferrite magnets, and also has a micro structure in
which the concentration of an R element is high in crystal grain boundaries,
and a method for producing such a high-performance ferrite magnet.
Accordingly, there is provided method for producing an anisotropic,
sintered ferrite magnet having a basic composition represented by the
following general formula:
(A1-xRx)O.n[ (Fe1-yMy)2O3] by atomic ratio,
wherein A is Sr or (Sr+Ba), and Sr is an indispensable element, R is at
least one of rare earth elements including Y, M is at least one element
selected from the group consisting of Co, Mn, Ni and Zn, and Co is an
indispensable element, and the percentage of Co in M is 50 atomic % or
more, and x, y and n are numbers meeting the following conditions:
0.01 =;x=0.4,
0.005 =sy=0.04, and
5=n=6
said anisotropic, sintered ferrite magnet having a magnetoplumbite-
type crystal structure,
said method comprising the steps of uniformly mixing at least one of
Sr compound and Ba compound with Fe compound; calcining the resultant
uniform mixture; adding the R element and the M element in the form of a
compound to the resultant calcined powder at a pulverization step after the
calcination thereof; molding the resultant pulverized powder in a in a
magnetic field; and sintering the resultant green body, wherein a hydroxide
of the R element is added as said R compound, and/or a hydroxide of the M
element is added as said M compound.
DESCRIPTION OF THE INVENTION
As a result of intense research in view of the above objects, the
inventors have found that the addition of an R element and an M element
by a post-addition method or a prior/post-addition method to ferrite having
a basic composition represented by (A1.xRx)O-n[(Fe1.yMy)2O3], wherein A is
Sr and/or Ba, R is at least one of rare earth elements including Y, and M is
at least one element selected from the group consisting of Co, Mn, Ni and
Zn can turn the ferrite to a higher-performance ferrite substantially having a
magnetoplumbite-type crystal structure with a higher squareness ratio
Hk/iHc and a reduced variation of shrink ratio, while keeping good
coercivity iHc (or good coercivity iHc and residual magnetic flux density
Br). The present invention has been completed based upon this finding.
Thus, the ferrite magnet according to the first embodiment of the
present invention has a basic composition represented by the following
general formula:
wherein A is Sr and/or Ba, R is at least one of rare earth elements including
Y, M is at least one element selected from the group consisting of Co, Mn,
Ni and Zn, and x, y and n are numbers meeting the following conditions:
and has a substantially magnetoplumbite-type crystal structure, the R
element and/or the M element being added in the form of a compound at a
pulverization step after calcination.
The ferrite magnet according to the second embodiment of the
present invention has a basic composition represented by the following
general formula:
(A1-xRx)O-n[(Fe1.yMy)2O3] by atomic ratio,
wherein A is Sr and/or Ba, R is at least one of rare earth elements including
Y, M is at least one element selected from the group consisting of Co, Mn,
Ni and Zn, and x, y and n are numbers meeting the following conditions:
and has a substantially magnetoplumbite-type crystal structure, the R
element and/or the M element being added in the form of a compound both
at a mixing step before calcination and at a pulverization step after
calcination.
In both cases, the concentration of the R element is preferably
higher in boundaries than in the magnetoplumbite-type crystal grains.
When the R element is La and the M element is Co, the ferrite magnet has a
residual magnetic flux density Br of 4,100 G or more, a coercivity iHc of
4,000 Oe or more and a squareness ratio Hk/iHc of 92.3% or more at 20°C.
Also, when the R element is La and the M element is Co plus Mn and/or Zn,
the ferrite magnet has a residual magnetic flux density Br of 4,200 G or
more, a coercivity iHc of 3,000 Oe or more and a squareness ratio Hk/iHc
of 93.5% or more at 20°C.
The method for producing a ferrite magnet according to the first
embodiment of the present invention, the ferrite magnet having a basic
composition represented by the following general formula:
(A1.xRx)O-n[(Fe1.yMy)2O3] by atomic ratio,
wherein A is Sr and/or Ba, R is at least one of rare earth elements including
Y, M is at least one element selected from the group consisting of Co, Mn,
Ni and Zn, and x, y and n are numbers meeting the following conditions:
0.01=x=0.4,
[x/(2.6n)]=sy=s[x/(1.6n)], and
5=sn=6,
and substantially having a magnetoplumbite-type crystal structure,
the method comprising the steps of uniformly mixing a compound of Sr
and/or Ba with an iron compound; calcining the resultant mixture; adding
the R element and/or the M element in the form of a compound to the
resultant calcined powder at a pulverization step thereof; and sintering the
resultant mixture.
The method for producing a ferrite magnet according to the second
embodiment of the present invention, the ferrite magnet having a basic
composition represented by the following general formula:
(A1.xRx)O-n[(Fe1.yMy)2O3] by atomic ratio,
wherein A is Sr and/or Ba, R is at least one of rare earth elements including
Y, M is at least one element selected from the group consisting of Co, Mn,
Ni.and Zn, and x, y and n are numbers meeting the following conditions:
0.01^x^0.4,
[x/(2.6n)]:sy 5sns6,
and substantially having a magnetoplumbite-type crystal structure,
the method comprising the steps of adding a compound of the R element
and/or the M element at a percentage of more thanO atomic % and 80
atomic % or less on an element basis at a step of uniformly mixing a
compound of Sr and/or Ba with an iron compound; calcining the resultant
uniform mixture; adding the remaining amount of the compound of the R
element and/or|the M element to the resultant calcined powder at a
pulverization step thereof; and sintering the resultant mixture.
In both cases, added as the R element compound is preferably an
oxide, a hydroxide, a carbonate or an organic acid salt of at least one
element selected from the group consisting of La, Nd, Pr and Ce. Also,
preferably added as the M element compound is an oxide, a hydroxide, a
carbonate or an organic acid salt of at least one element selected from the
group consisting of Co, Mn, Ni and Zn. It is also preferable to add only a
Co compound as the M element compound.
In a case where a high-performance ferrite magnet is produced by
the post-addition or prior/post-addition of the R element and the M element,
the resultant ferrite magnet shows extremely suppressed tendency of
decrease in a squareness ratio Hk/iHc as the amounts of the R element and
the M element added (values of x and y) increase, as compared with the
ferrite magnets obtained by the prior-addition method.
The post-addition or prior/gost-addition of the R element and the M
element may lead to the deterioration of Br and iHc and to variation in a
shrinkage ratio of a sintered body. To prevent the deterioration of Br and
iHc and the variation of a sintering shrinkage ratio, it is preferable to add an
Fe compound at the time of pulverization after calcination, in such an
amount as not to hinder the magnetic orientation of a green body along a
magnetic field during a process of forming the green body. Specifically,
the amount of the Fe compound post-added is preferably 0.1-11 weight %
on an iron element basis, based on the total amount of Fe contained in the
ferrite magnet.
It has been found that when the post-addition method is adopted, the
amounts of the R element and the M element (values of x and y) increase,
resulting in decrease in a molar ratio n, which in turn leads to the
deterioration of Br and iHc. It has also been found that when the molar
ratio n decreases, variations in the size of the resultant sintered body may
take place. The mechanism of decrease in the molar ratio n is as follows:
Investigation is conducted on the case of the production of a ferrite magnet
by the post-addition method, in which calcined ferrite powder having a
composition of SrO5.9Fe203, namely SrFen 8O18 7 (molar ratio n is 5.9), is
used, and a La oxide is added in the course of fine pulverization to
substitute about 20% of the Sr ion site with La. In this case, in order that
the ferrite magnet contains substantially the same number of Co atoms as
that of La atoms under charge compensation conditions, the corresponding
amount of a Co oxide is simultaneously added. Assuming that all of Co
added is contained as the M phase, the resultant ferrite sintered body has
Thus, the molar ratio n decreases from 5.9 at the stage of a calcined
powder to 4.9 by the post-addition of the La oxide and the Co oxide.
When the molar ratio n becomes less than 5, the relative percentage of
components corresponding to the Fe ion site bearing magnetism decreases,
resulting in drastic decrease in magnetic properties. At the same time, the
sintering shrinkage ratio indicating how much the size changes in the
course from the green body to the sintered body drastically changes,
resulting in large unevenness in the sizes of the resultant ferrite magnet
products.
The molar ratio n of the calcined powder may be set large in
advance, taking into consideration a decrease in the molar ratio n by the
post-addition method. However, this means is not effective.
Investigation will be made assuming that calcined powder having a
composition of SrO-n1Fe2O3 is used, and that both a La oxide and a Co
oxide are added at the time of fine pulverization to produce a high-
performance ferrite magnet having the following basic composition:
(Sr1-xLax)O-n2[(Fe1-yCoy)2O3] by atomic ratio,
wherein 0.01=x=0.4, and x/(2.6n2)=sy=sx/(1.6n2). If the values of x and y
were determined such that n1 = 6.5, and n2 = 5.9, the molar ratio n2 of the
resultant ferrite magnet would be 5.9, within a range (5-6) of the molar
ratio n suitable for the ferrite magnet. However, the ferrite magnet shows
extremely poor magnetic properties in this case. The reason therefor is
that when the molar ratio nx of the calcined powder is more than 6,
undesirable phases such as a-Fe2O3 other than the M phase appear in the
calcined powder. Because the undesirable phases are non-magnetic
phases, they reduce the magnetic orientation of a green body obtained by a
wet-molding method in a magnetic field. Thus, when the molar ratio nt of
the calcined powder exceeds 6, \Br, a squareness ratio Hk/iHc, etc.
drastically decrease, even if the molar ratio n2 of a ferrite magnet obtained
by the post-addition method is controlled within the range of 5-6.
Accordingly, it is preferable to add an iron compound such as iron
oxide, etc. by a post-addition method, to set the molar ratio n of a sintered
ferrite magnet obtained by the post-addition method and/or the prior/post-
addition method within the desired range of 5-6 without excessively
increasing the molar ratio n of the calcined powder. It is preferable that
the calcined powder has a molar ratio of 5-6 before the post-addition.
In addition, the post-addition method or the prior/post-addition
method is advantageous for the reason that it makes easy the mass
production of ferrite magnets. This is because the calcined powder of Sr
and/or Ba ferrite containing no or small amounts of R elements and M
elements can be used in the post-addition method or the prior/post-addition
method. More conveniently, by controlling the amounts of R elements
and M elements at the fine pulverization step after calcination, it is made
easy to produce ferrite magnets containing R elements and M elements
whose amounts differ depending on fine pulverization lots, namely ferrite
magnets having various magnetic properties.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a graph showing the magnetic properties of the ferrite
magnet in EXAMPLE 1;
Fig. 2 is a graph showing the correlation between the amount of
Fe3O4 added and magnetic properties in the ferrite magnets in EXAMPLES
2 and 3;
Fig. 3 is a schematic view explaining the sintering shrinkage ratio;
Fig. 4 is a graph showing the correlation between the amount of
Fe3O4 added and a sintering shrinkage ratio in the ferrite magnets in
EXAMPLES 2 and 3;
Fig. 5 is a graph showing the effectiveness of Fe2O3 in the ferrite
magnet in EXAMPLE 5;
Fig. 6 is a graph showing the correlation between the amount of
Fe3O4 added and magnetic properties in the ferrite magnet in EXAMPLE 6;
Fig. 7 is a graph showing the results of EPMA analysis of the ferrite
magnet produced by the prior-addition method in COMPARATIVE
EXAMPLE 4;
Fig. 8 is a graph showing the results of EPMA analysis of the ferrite
magnet produced by the post-addition method in EXAMPLE 1;
Fig. 9 is a graph showing the results of EPMA analysis of the ferrite
magnet produced by the post-addition method in EXAMPLE 2;
Fig. 10 is a graph showing the results of EPMA analysis of the
ferrite magnet produced by the prior/post-addition method in EXAMPLE
10;
Fig. 11 is a graph showing the magnetization-temperature curves of
the ferrite magnets produced by the prior-addition method;
Fig. 12 is a graph showing the magnetization-temperature curves of
the ferrite magnets produced by the post addition method and the
prior/post-addition method;
Fig. 13 is a graph showing the correlation between a squareness
ratio and resistance to demagnetization in the ferrite magnet produced by
the post-addition method in EXAMPLE 24; and
Fig. 14 is a graph showing the correlation between a squareness
ratio and resistance to demagnetization in the ferrite magnet produced by
the prior-addition method in COMPARATIVE EXAMPLE 8.
THE BEST MODE FOR CONDUCTING THE INVENTION
[1] Ferrite magnet
The basic composition of the ferrite magnet to which the present
invention is applicable is represented by the following general formula:
(A1.xRx)O-n[(Fe1.yMy)2O3] by atomic ratio,
wherein A is Sr and/or Ba R is at least one of rare earth elements including
Y,M is at least one element selected from the group consisting of Co, Mn,
Ni and Zn, and x, y and n are numbers meeting the following conditions:
0.01=;x=0.4,
[x/(2.6n)]=y=[x/(1.6n)], and
5=n=6.
To impart good magnetic properties to the ferrite magnet of the
present invention, the value of n (molar ratio) should be between 5 and 6.
When the value of n exceeds 6, undesirable phases such as a-Fe2O3 other
than the magnetoplumbite phase are generated, resulting in drastic decrease
in magnetic properties. On the other hand, when the value of n is less
than 5, Br of the ferrite magnet drastically decreases.
The value of x is between 0.01 and 0.4. When the value of x is
less than 0.01, sufficient effects of the post-addition method or the
prior/post-addition method cannot be obtained. On the other hand, when
the value of x exceeds 0.4, the magnetic properties of the ferrite magnet
rather decrease.
To investigate the permissible range of a ratio of the R element / the
M element added in connection with charge compensation, Sr, La and Co
were selected as the A element, the R element and the M element,
respectively, and SrCO3, Fe2O3, La2O3, and Co3O4 were formulated in such
proportions as to provide the following basic composition:
(Sr1.xLax)On[(Fe1.yCoy)2O3] by atomic ratio,
wherein x = 0.15, y = 0.77-2.08 x 10 2, and n = 6.0,
wet-mixed, and then calcined at 1200°C for 2 hours. The magnetic
properties of the resultant coarse powder were measured. It has thus been
found that there is no substantial deterioration in magnetic properties, as
long as the ratio of x/ny is within the range of 1.6-2.6, not limited to the
conditions under which the charge balance is fully kept, namely to a ratio
of x to y satisfying the relation of y = x/2n. When the value of y deviates
from x/(2.0n), there is likelihood that Fe2+ is contained, though there are no
problems. On the other hand, when the ratio of x/ny exceeds 2.6 or is less
than 1.6, remarkable decrease in magnetic properties is appreciated.
Accordingly, the ratio of x/ny should be between 1.6 and 2.6. This
condition may be converted to the formula of y as follows:
[x/(2.6n)]«sy=s[x/(1.6n)].
In typical example, the preferred range of y is 0.04 or less,
particularly 0.005-0.03. Even when the contents of the R element and the
M element meet the equation of y = x/(2.0n), part of the R element and/or
the M element may be accumulated in high concentration in the vicinity of
grain boundaries, without causing any problems.
In any of the post-addition method and the prior/post-addition
method, the R element is preferably at least one selected from the group
consisting of ta, Nd, Pr and Ce. In one example of the ferrite magnets of
the present invention, the percentage of La in R is preferably 50 atomic %
or more, more preferably 70 atomic % or more, particularly preferably 99
atomic % or more to improve saturation magnetization thereof. The R
element may be composed of La only.
In another example of the ferrite magnets of the present invention,
the total percentage of Nd, Pr and/or Ce in R is preferably 50 atomic % or
more, more preferably 70 atomic % or more, particularly preferably 99
atomic % or more to improve saturation magnetization thereof.
In a further example of the ferrite magnets of the present invention,
the total percentage of one or more of La, Nd, Pr and Ce in R is preferably
50 atomic % or more, more preferably 70 atomic % or more, particularly
preferably 99 atomic % or more to improve saturation magnetization
thereof.
The M element is preferably composed of Co only, or Co plus Mn
and/or Ni. Particularly to have higher Br and iHc than those of the
conventional ferrite magnets, it is preferable to select Co plus Mn and/or Ni
as M. The addition of Mn contributes to provide ferrite magnets with
good magnetic properties, even when the R element is added in a smaller
amount than the level that would be required by the charge compensation
conditions but for Mn.
When Mn is contained, the content of Mn is preferably 0.4
atomic % or more, assuming that the total amount of Mn and the other M
element is 100 atomic %. For instance, when M consists of Co and Mn,
the content of Mn is preferably 0.4-75 atomic %, more preferably 0.7-60
atomic %, particularly preferably 1-50 atomic %, assuming that Co + Mn is
100 atomic %. When the content of Mn is less than 0.4 atomic %,
improvement in Br_by adding Mn cannot be appreciated. On the other
hand, when the content of Mn exceeds 75 atomic %, iHc of the ferrite
magnet drastically decreases.
Also, when Co + Mn +Ni (Zn) are selected as the M elements, the
content of Mn is preferably 0.4-75 atomic %, more preferably 0.7-60
atomic %, particularly preferably 1-50 atomic %, assuming that the total
amount of Co + Mn +Ni (Zn) is 100 atomic %.
Further, when M consists of Co and Ni, the percentage of Ni in M is
preferably 10-75 atomic %, more preferably 10-60 atomic %, particularly
preferably 10-50 atomic %, based on the total amount (100 atomic %) of
the M elements, to have higher Br and iHc than those of the conventional
ferrite magnets. When the percentage of Ni in M is less than 10 atomic %,
remarkable improvement in Br cannot be obtained. On the other hand,
when the percentage of Ni exceeds 75 atomic %, iHc of the ferrite magnet
decreases drastically.
Further, when Mn and/or Ni is selected as M, the content of Mn is
preferably 0.4-75 atomic %, more preferably 0.7-60 atomic %, particularly
preferably 1-50 atomic %, based on the total amount (100 atomic %) of Mn
+ Ni, so that the ferrite magnet can have higher magnetic properties than
those of the conventional ferrite magnets.
The ferrite magnet obtained by the post-addition method or
prior/post-addition method of the present invention substantially has a
magnetoplumbite-type crystal structure. When the R element is La and
the M element is Co, the ferrite magnet has a residual magnetic flux density
Br of 4,100 G or more, a coercivity iHc of 4,000 Oe or more and a
squareness ratio Hk/iHc of 92.3% or more at 20°C. Also, when the R
element is La and the M element is Co plus Mn and/or Zn, the ferrite
magnet has a residual magnetic flux density Br of 4,200 G or more, a
coercivity iHc of 3,000 Oe or more and a squareness ratio Hk/iHc of 93.5%
or more at 20° C.
The Hk used herein, which is a parameter measured to obtain the
squareness ratio, is a value on the H axis in a graph of a 4pI-H curve,
wherein 4pl represents the intensity of magnetization and H represents the
intensity of a magnetic field, at a position in the second quadrant where 4pI
is 0.95 Br. The squareness ratio is defined as a value of Hk/iHc obtained
by dividing Hk by iHc in the above demagnetization curve.
In the ferrite magnet of the present invention, the M element is
sufficiently dissolved in the magnetoplumbite-type ferrite crystal grains,
though the concentration of the M element tends to be higher in the crystal
grain boundaries than in the crystal grains.
[2] Production method
In the standard process for producing ferrite magnets essentially
comprising the steps of mixing of starting material powders -» calcination
-> fine pulverization of calcined->powder -> molding -» sintering -»
machining, the basic composition of the ferrite magnet is substantially
achieved at the fine pulverization step and thereafter.
Preferable as materials for supplying the R elements are oxides or
hydroxides of R elements, particularly hydroxides. Specifically, one or
more of oxides such as La2O3, hydroxides such as La(OH)3, carbonate
hydrates such as La2(CO3)3-8H2O, organic acid salts such as
La(CH3CO2)31.5H2O, La2(C2O4)310H2O, etc. may be used. Oxides,
hydroxides, carbonates and organic acid salts of R elements (Nd, Pr, Ce)
other than La may also be used. Further, one or more of oxides,
hydroxides, carbonates and organic acid salts of mixtures of rare earth
elements (La, Nd, Pr and Ce) may also be used. The addition of
hydroxides of R elements tends to improve Br, iHc and a squareness ratio
Hk/iHc than the addition of oxides thereof. In addition, inexpensive
Misch metals (mixed rare earth elements) containing 50 atomic % or more
of one or more of La, Nd, Pr and Ce may also be used.
Compounds of M elements are preferably added in the form of
oxides or hydroxides, particularly hydroxides. Specifically, one or more
of oxides such as Co3O4; hydroxides such as Co(OH)2, Co3O4n1HjO,.
wherein n1 is a positive number; carbonates such as CoCO3; basic
carbonates such as m2CoCO3m3Co(OH)2-m4H2O, wherein m2, m3 and m4
are positive numbers, may be used. Oxides, hydroxides or carbonates of
Mn, Ni or Zn may also be used. The addition of hydroxides of M
elements tends to improve Br, iHc and a squareness ratio Hk/iHc than the
addition of oxides thereof.
In both of the post-addition method and the prior/post-addition
method, it is preferable to add iron compounds at the time of pulverization
(particularly fine pulverization) after calcination to adjust the molar ratio n.
The addition of iron compounds at the time of pulverization serves to
arbitrarily adjust the values of y and n at the time of fine pulverization.
The iron compounds post-added may be one or more oxides
selected from Fe3O4, Fe2O3 (a-Fe2O3, Y~Fe2O3) and FeO. Also, hydroxides
of iron may be one or more of Fe(OH)2, Fe(OH)3 and FeO(OH).
The amount of the iron compound post-added is preferably 0.1-11
weight % on an iron element basis, per the total amount of Fe added.
When the amount of the iron compound post-added is less than 0.1
weight %, sufficient effects of addition cannot be obtained. On the other
hand, when the amount of the iron compound post-added exceeds 11
weight %, orientation of ferrite particles at the time of molding in a
magnetic field is reduced, resulting in drastic decrease in Br.
The post-addition of the iron compound serves to increase the molar
ratio n, resulting in drastic improvement in a squareness ratio. For
instance, when the R element is La and the M element is Co, the ferrite
magnet has a squareness ratio Hk/iHc of 92.3% or more at 20°C. Also,
when the R element is La and the M element is Co plus Mn and/or Zn, the
ferrite magnet has a squareness ratio Hk/iHc of 93.5% or more at 20°C.
In both cases, the resultant ferrite magnets have a stable shrinkage ratio.
Also at the pulverization step after calcination, spinel-type ferrite
compounds such as CoOFe203 instead of the Co compound, MnOFe203
instead of the Mn compound, ZnO-Fe2O3 instead of the Zn compound, (Co,
Mn)OFe203 instead of the Co compound and the Mn compound, (Mn,
Zn)OFe203 instead of the Mn compound and the Zn compound, (Co,
Zn)OFe203 instead of the Co compound and the Zn compound, and (Co,
Mn, Zn)OFe203 instead of the Co compound, the Mn compound and the
Zn compound may be added to suppress decrease in the molar ratio n by
the post-addition method.
At the wet-fine pulverization step after calcination, powder of
compounds of the R elements and/or the M elements, and if necessary,
powder of the iron compounds are added in such amounts as to obtain the
formulation equal to the final composition of the ferrite sintered body.
Wet fine pulverization is carried out until the average diameter of the
powder mixture becomes 0.4-0.9 mm. A slurry of finely pulverized
powder is concentrated or dried, crumbled, milled, wet-molded and then
sintered.
When pulverization is carried out to an average diameter of less
than 0.4 mm, undesirable crystal grain growth takes place at the sintering
step, resulting in decrease in coercivity and the deterioration of water
removal characteristics at the wet-molding step. Also, when the average
diameter of the powder exceeds 0.9 mm, there are a lot of coarse crystal
grains in the structure of the ferrite sintered body.
It is preferable to add SiO2, .CaO2 GaCO3, etc. as elements for
controlling a sintering phenomenon at the pulverization step after
calcination. SiO2 is an additive for suppressing crystal grain growth at the
sintering step, and the amount of SiO2 added is preferably 0.05-0.5
weight %, assuming that the basic composition of the ferrite magnet is 100
weight %. When the amount of SiO2 added is less than 0.05 weight %,
excessive crystal grain growth takes place at the sintering step, resulting in
decrease in coercivity. On the other hand, when the amount of SiO2
added exceeds 0.5 weight %, crystal grain growth is excessively suppressed,
resulting in insufficient improvement in orientation that occurs
simultaneously with the crystal grain growth, which leads to decrease in Br.
CaO is an element for accelerating the crystal grain growth, and the
amount of CaO added is preferably 0.35-0.85 weight %, assuming that the
basic composition of the ferrite magnet is 100 weight %. When the
amount of CaO added exceeds 0.85 weight %, excessive crystal grain
growth takes place at the sintering step, resulting in decrease in coercivity.
On the other hand, when the amount of CaO added is less than 0.35
weight %, crystal grain growth is excessively suppressed, resulting in
insufficient improvement in orientation that occurs simultaneously with the
crystal grain growth, which leads to decrease in Br.
The ferrite magnet produced by the prior/post-addition method is
likely to have substantially an intermediate microstructure between the
microstructure of the prior-addition method and that of the post-addition
method. In the prior/post-addition method, when the R element added at
the pulverization step, particularly fine pulverization step, after calcination
is 20 atomic % or more, particularly 40 atomic % or more, and less than
100 atomic %, for instance, 50-80 atomic %, per the total amount of the R
element added, good improvement in a squareness ratio Hk/iHc can be
achieved. Also, in the prior/post-addition method, when the M element
added at the pulverization step, particularly fine pulverization step, after
calcination is 20 atomic % or more, particularly 40 atomic % or more, and
less than 100 atomic % per the total amount of the M element added,
remarkable improvement in a squareness ratio Hk/iHc can be achieved.
The important requirements for obtaining the high-performance
ferrite magnet are that the composition of the ferrite powder used should be
properly controlled, and that the ferrite powder should not be agglomerated
in a slurry. As a result of investigation to achieve a state in which each
particle of the ferrite powder exists independently in the slurry, it has been
found that the agglomeration of ferrite powder is destroyed by drying or
concentrating a ferrite powder slurry obtained by the wet-fine pulverization
of ferrite powder, adding a dispersant to the resultant high-concentration
slurry and milling the slurry, resulting in improvement in orientation of
ferrite magnet powder, which leads to improvement in magnetic properties.
It has also been found that by adding a dispersant to the slurry at a mixing
step, good dispersion can be achieved due to surface modification of ferrite
magnet powder by the adsorption of the dispersant, resulting in further
improvement in a magnetic force of the ferrite magnet.
Known as dispersants are surfactants, higher aliphatic acids, higher
aliphatic acid soap, aliphatic acid esters, etc. It has been found that the
dispersion of ferrite particles can be improved by using a polycarboxylic
acid dispersant, one of anionic surfactants, effectively preventing the
agglomeration of ferrite particles. There are many types of
polycarboxylic acid dispersants, and particularly effective for improvement
in the dispersion of ferrite particles among them is an ammonium salt of
polycarboxylic acid.
The amount of the dispersant added is preferably 0.2-2 weight %,
per a solid component in the fine powder slurry. When the amount of the
dispersant added is less than 0.2 weight %, effects of adding the dispersant
cannot be obtained. On the other hand, when it exceeds 2 weight %, the
residual magnetic flux density of the ferrite magnet rather decreases.
The present invention will be described in detail below referring to
EXAMPLES, without intention of restricting the scope of the present
invention thereto.
REFERENCE EXAMPLES 1-9, COMPARATIVE EXAMPLES 1-3
SrCO3, Fe2O3, oxides of R elements and oxides of M elements were
formulated to provide the following basic composition:
(Sr1.xRx)O-n[(Fe1.yMy)2O3] by atomic ratio,
wherein n = 6.0, x = 0.15, and y = x/2n = 0.0125, wet-mixed, and then
calcined at 1200°C for 2 hours in the air. La was selected as the R
element under the criterion that La has an ion radius close to a radius of an
Sr ion. Also, Ti, V, Mn, Co, Ni, Cu and Zn were selected as the M
elements under the criterion that they had ion radii close to a radius of an
Fe ion.
As COMPARATIVE EXAMPLE 1, a ferrite composition in which n
= 6.0 and x = y = 0 in the above basic composition, namely SrO6.0Fe203,
was calcined in the same manner. Also, as COMPARATIVE EXAMPLES
2 and 3, calcined powder having the same composition as in REFERENCE
EXAMPLES except that the R element was La and that the M element was
Cu or Co + Cu was produced.
Each calcined powder was coarsely pulverized in a dry state by a
roller mill, and each of the resultant coarse powder was measured with
respect to magnetic properties by a vibration-type magnetometer. The
highest intensity of a magnetic field in which measurement was carried out
was 12 kOe, and a saturation magnetization as and He were determined by
a-l/H2 plot. The resultant phases of the coarse powder were identified by
X-ray diffraction, with the results summarized in Table 1. It is
appreciated from Table 1 that when Cu was not contained as the M element,
only X-ray diffraction peaks for a magnetoplumbite phase (M phase) were
observed in any powder. It is also appreciated from Table 1 that when La
was selected as the R element, and Mn, Mn + Co, Ni or Ni + Co was
selected as the M element, the resultant calcined powder had higher as (or
higher as and He) than that in COMPARATIVE EXAMPLE 1, suggesting
that such calcined powder had a potential that a high-performance, bulk
ferrite magnet could be formed therefrom by sintering.
In the present invention, combinations of La and Mn + Ni, La and
Mn + Co + Ni, La and Mn + Co + Zn, La and Co + Ni + Zn, La and Mn +
Ni + Zn, and La and Mn + Co + Ni + Zn may further by used. Among
them, when Co is contained, the percentage of Co in the M elements is
preferably 10 atomic % or more to have higher Br and iHc than those of
conventional ferrite magnets.
2 hours in the air. The calcined powder was coarsely pulverized in a dry
state by a roller mill, and then finely pulverized in a wet state by an attritor
to produce a slurry containing fine powder of 0.80 mm in average diameter.
At an early stage of the fine pulverization of each coarse powder, 0-2.5
weight % of La2O3 and 0-2.3 weight % of CoO, based on the weight of the
coarse powder, were added. Also, 1.3 weight % of Cr2O3 was added at an
early stage of the fine pulverization of coarse powder to produce a slurry as
a comparative material. In any cases, 0.50 weight % of SrCO3, 0.30
weight % of SiO2 and 0.80 weight % of CaCO3 (0.45 weight % as CaO),
based on the weight of the coarse powder, were added as sintering aids.
For instance, the final basic composition obtained when 2.50 weight % of
La2O3 and 1.15 weight % of CoO were added approximately corresponds to
the following formula:
(Sr1.xLax)0-n[(Fe1.yCoy)203] by atomic ratio,
wherein x = 0.15, y = x/2n, and n = 5.25.
A slurry containing each fine powder of 0.8 mm was wet-molded in
a magnetic field of 10 kOe, and each of the resultant green bodies was
sintered at 1210-1230°C for 2 hours. Each of the resultant sintered bodies
was machined to a shape of about 10 mm x 10 mm x 20 mm to measure
magnetic properties at 20°C by a B-H tracer. The results are shown in Fig.
1.
It is clear from Fig. 1 that the addition of 2.50 weight % of La2O3
and 1.15 weight % of CoO (indicated by "V") greatly improves iHc as
compared with no addition (indicated by "O"), with extremely smaller
decrease in Br in a high iHc region than in the case of the addition of Cr2O3
that is usually added to increase iHc (indicated by " X "). Further, iHc was
low when only CoO was added (indicated by "A, ?"), or when the
balance of charge compensation was destroyed (indicated by "O").
This EXAMPLE has proved that by utilizing the post-addition
method in which the La compound and the Co compound are added to
provide the Sr ferrite magnet with the desired basic composition, at the
time of fine pulverization after the preparation of coarse calcined powder,
the Sr ferrite magnet has higher Br and iHc than the original Sr ferrite
magnet.
Next, observation by a scanning-type electron microscope (SEM)
was carried out on samples cut away in an appropriate size from sintered
bodies prepared by adding La2O3 and CoO at a fine pulverization step.
Table 2 shows the results of SEM analysis of magnetoplumbite-type ferrite
crystal grains and crystal grain boundaries in these samples. It is clear
from Table 2 that La (R element) and Co (M element) are fully dissolved in
the magnetoplumbite-type ferrite crystal grains, though they also exist in
crystal grain boundaries in large amounts. Further, analysis by SEM, etc.
at 20 sites in each of the crystal grain boundaries and the crystal grains of
this sample have revealed that La (R element) and/or Co (M element) tend
to be higher in concentration in the crystal grain boundaries than in the
magnetoplumbite-type ferrite crystal grains. This clearly has a close
relation to the fact that the ferrite magnet was prepared by the post-addition
method in which La2O3 and CoO were added for adjustment to the basic
composition of the sintered body at the fine pulverization step after
Though this EXAMPLE indicates a case where R = La and M = Co,
it should be noted that ferrite magnets formed from combinations of other
R elements and other M elements would also have high coercivity iHc (or
high coercivity iHc and residual magnetic flux density Br), as long as they
have the same microstructures as in this EXAMPLE.
EXAMPLE 2
This EXAMPLE shows that variation of magnetic properties and
shrinkage ratio decreases by the addition of an iron compound at a fine
pulverization step after calcination, in the production of ferrite magnets by
a post-addition method.
SrCO3 and Fe2O3 were formulated to provide a basic composition of
SrO-nFe2O3, wherein n = 5.9, wet-mixed, and then calcined at 1250°C for 2
hours in the air. The calcined powder was coarsely pulverized in a dry
state by a roller mill, and then finely pulverized in a wet state by an attritor
to produce a slurry containing fine powder of 0.8 mm in average diameter.
Added at an early stage of the fine pulverization of the coarse powder were
2.5 weight % of La2O3, 1.2 weight % of Co3O4 and 2-8 weight % of Fe3O4
(magnetite), based on the weight of the coarse powder. Further, 0.1
weight % of SrCO3,1.0 weight % of CaCO3 and 0.3 weight % of SiO2,
based on the weight of the coarse powder, were added as sintering aids.
Each of the resultant fine powder slurries were wet-molded in a magnetic
field of 10 kOe, and each of the resultant green bodies was sintered at
1210-1230°C for 2 hours. The resultant sintered body had a basic
composition approximately corresponding to the following formula:
(Sr1.xLax)O-n[(Fe1.yCoy)2O3] by atomic ratio,
wherein x = 0.15, y = x/2n, and n = 5.32-5.67.
The resultant sintered body was machined to a shape of about 10
mm x 10 mm x 20 mm to measure magnetic properties at 20°C by a B-H
tracer. The results are shown in Fig. 2, in which the axis of ordinates
represents Br (kG), and the axis of abscissas represents iHc (kOe).
EXAMPLE 3
Ferrite magnets having the following basic composition:
(Sr1.xLax)O-5.20[(Fe1.yCoy)2O3] by atomic ratio,
wherein x = 0.15, and y = x/2n, were prepared in the same manner as in
EXAMPLE 2 except for adding no Fe3O4. The resultant ferrite magnets
had a molar ratio n decreased to 5.20. the magnetic properties measured
in the same manner as in EXAMPLE 2 are shown in Fig. 2.
It is clear from Fig. 2 that magnetic properties are improved when
2-8 weight % of Fe3O4 was added than when the amount of Fe3O4 added
was 0 weight %. For instance, the addition of 6 weight % of Fe3O4
contributed to increase in Br by about 100 G in a case where there was no
change in iHc, and increase in iHc by about 600 Oe in a case where there
was no change in Br, as compared to no addition of Fe3O4 (EXAMPLE 3).
It has further been found by investigation in connection with Fig. 2
that not only improvement in Br, iHc and a squareness ratio Hk/iHc but
also stabilization of shrinkage ratio can be achieved by the addition of 0.1-
11 weight % (on an Fe element basis) of Fe3O4 as compared to no addition
of Fe3O4 (EXAMPLE 3). Also, when the amount of Fe3O4 added was 0.1-
11 weight % (on an Fe element basis), high-coercivity, high-performance
ferrite magnets having Br of 4,150-4,400 G, iHc of 4,050-4,500 Oe, and a
squareness ratio Hk/iHc of 94.5-96% were obtained.
Next, correlation between the amount of Fe3O4 added and a
shrinkage ratio will be investigated. As shown in Fig. 3, the shrinkage
ratio includes a shrinkage ratio (Sh//) along the direction of magnetic
anisotropy (Mag.) substantially identical to the direction of a magnetic field
applied in a wet-molding process, and a shrinkage ratio (Sh_L) along the
direction vertical thereto, each being defined as follows:
(Sh//) = (h1-h2)/h1xl00(%),
(Sh-L) = (lrl2) / \ x 100 (%),
11 Length of green body,
12: Length of sintered body,
hx: thickness of green body, and
h2: thickness of sintered body.
With respect to ferrite magnets obtained in EXAMPLES 2 and 3, the
dependency of the correlation of iHc and (Sh1) on the amount of Fe3O4
added (molar ratio n) is shown in Fig. 4. In Fig. 4, five plots (O) in a
case where 8.0 weight % of Fe3O4 was added indicate a range of the
variation of (Sh_L) at a sintering temperature of 1210-1230°C A(Shl), a
range of variation of (Sh_L) at each amount of Fe3O4 added, is defined by
the formula: A(Shl) = (maximum of Sh_L) - (minimum of Sh_L). Fig. 4
verifies that as the amount of Fe3O4 added (molar ratio n) increases, the
range of variation of shrinkage ratio A(Sh_L) decreases. Further, when the
amount of Fe3O4 added increases to 15 weight %, the molar ratio n can be
increased to about 6, and A(Sh_L) can be made extremely small. Thus, in
the ferrite magnets formed by the post-addition method, (Shi) and A(Sh_L)
can freely be controlled within the ranges of (Sh_L) = 11-13.5% and A(Shl)
= 0.05-0.9%. To suppress dimensional variations of ferrite magnet
products, A(Sh-L) is preferably 0.05-0.8%, more preferably 0.05-0.5%,
particularly preferably 0.05-0.3%.
Further, A(Shl / Shi I), a range of variation of (Shi / Sh//) at each
amount of Fe3O4 added, is defined by the formula: A(Sh_L / Sh//) =
(maximum of Shi / Sh//) - (minimum of Shi / Sh//). It has been verified
from measurement results related to Fig. 4 that as the amount of Fe3O4
added (molar ratio n) increases, the range of variation of shrinkage ratio
A(Shl / Sh//) decreases. Further, when the amount of Fe3O4 added
increases to 15 weight %, the molar ratio n can be increased to about 6, and
A(Shl / Sh//) can be made extremely small. Thus, in the ferrite magnets
formed by the post-addition method, (Shi / Sh//) and A(Shl / Sh//) can

freely be controlled within the ranges of (Shi / Sh//) = 1.6-2.4 and A(Shl /
Sh//) = 0.05-0.30. To suppress dimensional variations of ferrite magnet
products, as the molar ratio n nears about 6, D(Sh_L / Sh//) can be made
small, with (Shi / Sh//) controlled to 1.9-2.2. D(Sh± / Sh//) is controlled
to more preferably 0.05-0.20, further preferably 0.05-0.15, particularly
preferably 0.05-0.10.
COMPARATIVE EXAMPLE 4
La and Co were selected as the R element and the M element,
respectively, and SrCO3, Fe2O3, La2C)3 and Co3O4 were formulated to
provide the following basic composition:
(Sr1.xLax)O-n[(Fe1.yCoy)2O3] by atomic ratio,
wherein x = 0-0.5, y = x/2n, and n = 5.85, wet-mixed, and then calcined at
1200°C for 2 hours in the air. The calcined powder was coarsely
pulverized in a dry state by a roller mill, and then finely pulverized in a wet
state by an attritor to produce a slurry containing fine powder of 0.8 \im in
average diameter. Added as sintering aids at an early stage of the fine
pulverization of the coarse powder were 0.40 weight % of SiO2 and 0.80
weight % of CaCO3 (0.45 weight % as CaO), based on the weight of the
coarse powder. Each of the resultant fine powder slurries was wet-molded
in a magnetic field of 10 kOe, and each of the resultant green bodies was
sintered at 1210-1230°C for 2 hours. Each of the resultant sintered bodies
was machined to a shape of about 10 mm x 10 mm x 20 mm.
SrCO3 and Fe2O3 were formulated to provide a basic composition of
SrOnFe203, wherein n = 5.6, wet-mixed, and then calcined at 1250°C for 2
hours in the air. Thereafter, 2-8 weight % of Fe3O4 (magnetite) was added
at an early stage of the fine pulverization step of coarse powder by a post-
addition method in the same manner as in EXAMPLE 2, to produce sintered
ferrite magnets. Each of the resultant sintered bodies substantially had the
following composition:
(Sr1-xLax)O-n[(Fe1.yCoy)2O3] by atomic ratio,
wherein x = 0.15, y = x/2n, and n = 5.01-5.35.
Among them, ferrite magnets having n of 5.01-5.20 had
substantially as high magnetic properties as those of EXAMPLE 3, fully
satisfactory for practical applications. Also, the ferrite magnets having n
exceeding 5.20 had substantially as high magnetic properties as those of the
equimolar-ratio ferrite magnets obtained in EXAMPLE 2.
COMPARATIVE EXAMPLE 5
Ferrite magnets were produced in the same manner as in EXAMPLE
2 except that a molar ratio n in the basic composition of SrOnFe2O3 was
controlled to 6.3 at the time of mixing before calcination, and that 6
weight % of Fe3O4 (magnetite) was added at an early stage of the fine
pulverization step of coarse powder by a post-addition method, and their
magnetic properties were measured at 20°C by a B-H tracer. The resultant
ferrite magnet substantially had the following composition:
(Sr1.xLax)O-5.94[(Fe1.yCoy)2O3] by atomic ratio,
wherein x = 0.15, and y = x/2n.
The magnetic properties of these ferrite magnets were so low that
they could not be plotted in Fig. 2. Considerable precipitation of a-Fe2O3,
which may be considered due to insufficient ferritization reaction, was
observed in the calcined powder of this COMPARATIVE EXAMPLE. It
was confirmed that the precipitation of a-Fe2O3 deteriorated the magnetic
properties of the final ferrite magnets.
EXAMPLE 5
SrCO3 and Fe2O3 were formulated to provide a basic composition of
SrOnFe203, wherein n = 5.9, wet-mixed, and then calcined at 1250°C for 2
hours in the air. The calcined powder was coarsely pulverized in a dry
state by a roller mill, and then finely pulverized in a wet state by an attritor
to produce a slurry containing fine powder of 0.8 mm in average diameter.
Added at an early stage of the fine pulverization of each coarse powder
were 2.5 weight % of La2O3 and 1.2 weight % of Co3O4, together with 6
weight % of Fe3O4 (magnetite) or 6.2 weight % of Fe2O3 (hematite), based
on the weight of the coarse powder. Further, 0.3 weight % of SrCO3,1.0
weight % of CaCO3 and 0.3 weight % of SiO2, based on the weight of the
coarse powder, were added as sintering aids at an early stage of the fine
pulverization of each coarse powder. Each of the resultant two fine
powder slurries was wet-molded in a magnetic field of 10 kOe, and each of
the resultant green bodies was sintered at 1210-1230°C for 2 hours. Each
of the resultant two sintered bodies substantially had the following formula:
(Sr1.xLax)O-n[(Fe1.yCoy)2O3] by atomic ratio,
wherein x = 0.15, y = x/2n, and n = 5.55 (when 6 weight % of Fe3O4 was
added) or n = 5.50 (when 6.2 weight % of Fe2O3 was added).
Each of the resultant sintered bodies was machined to a shape of
about 10 mm x 10 mm x 20 mm to measure magnetic properties at 20° C by
a B-H tracer. The results are shown in Fig. 5, in which the axis of
ordinates represents Br (kG), and the axis of abscissas represents iHc
(kOe).
It has been found from Fig. 5 and its related investigation that the
addition of 6 weight % of Fe3O4 (magnetite) or 6.2 weight % of Fe2O3
(hematite) contributes to remarkable improvement in magnetic properties,
D(Sh_L), and D(Sh_L / Sh//) as compared with EXAMPLE 3. Thus, Fe2O3
(hematite) is as effective as Fe3O4 (magnetite) in the post-addition method.
EXAMPLE 6
SrCO3 and Fe2O3 were formulated to provide a basic composition of
SrOnFe2O3, wherein n = 5.9, wet-mixed, and then calcined at 1250°C for 2
hours in the air. The calcined powder was coarsely pulverized in a dry
state by a roller mill, and then finely pulverized in a wet state by an attritor
to produce a slurry containing fine powder of 0.8 mm in average diameter.
Added at an early stage of the fine pulverization of each coarse powder
were 2.5 weight % of La2O3, 0.6 weight % of Co3O4 and 0.6 weight % of
ZnO, together with 2-8 weight % of Fe3O4 (magnetite), based on the weight
of the coarse powder. Further, 0.1 weight % of SrCO3,1.0 weight % of
CaCO3 and 0.3 weight % of SiO2, based on the weight of the coarse powder,
were added as sintering aids at an early stage of the fine pulverization of
each coarse powder. Each of the resultant two fine powder slurries wa,s
wet-molded in a magnetic field of 10 kOe, and each of the resultant green
bodies was sintered at 1210-1230°C for 2 hours. Each of the resultant
sintered bodies substantially had the following formula:
(Sr1-xLax)O-n[(Fe1-yCo05yZi05y)2O3] by atomic ratio,
wherein x = 0.15, y = x/2n, and n = 5.32-5.67.
Each of the resultant sintered bodies was machined to a shape of
about 10 mm x 10 mm x 20 mm to measure magnetic properties at 20° C by
a B-H tracer. The results are shown in Fig. 6, in which the axis of
ordinates represents Br (kG), and the axis of abscissas represents iHc
(kOe).
EXAMPLE 7
Ferrite magnets were produced in the same manner as in EXAMPLE
6 except for no post-addition of Fe3O4 to measure their magnetic properties.
The ferrite sintered bodies obtained without post-addition of Fe3O4
substantially had the following formula:
(Sr1-xLax)O-n[(Fe1-yCo05yZn05y)2O3] by atomic ratio,
wherein x = 0.15, y = x/2n, and n = 5.20.
The magnetic properties of the ferrite sintered bodies are shown in
Fig. 6. It is clear from Fig. 6 that magnetic properties are improved when
2-8 weight % of Fe3O4 was post-added (EXAMPLE 6) than when no Fe3O4
was added (EXAMPLE 7). For instance, the addition of 6-8 weight % of
Fe3O4 contributed to increase in Br by about 100 G in a case where there
was no change in iHc, and increase in iHc by about 600 Oe in a case where
there was no change in Br, as compared to no addition of Fe3O4.
It has further been found from related investigation that not only
improvement in magnetic properties but also stabilization of shrinkage ratio
can be achieved by the addition of 0.1-11 weight % (on an Fe element
basis) of Fe3O4 as compared to no addition of Fe3O4 (EXAMPLE 7).
Specifically, the post-addition of Fe3O4 could provide high-Br, high-
performance ferrite magnets with Br of 4,250-4,450 G, iHc of 3,000-3,800
Oe, and a squareness ratio Hk/iHc of 94.5-97%.
(Sh±) and D(Sh_L) of the ferrite magnets can freely be controlled
within the ranges of (Sh±) = 11-13.5% and D(Shl) = 0.05-0.9%. To
suppress dimensional variations of ferrite magnet products, D(ShJ_) can be
made preferably 0.05-0.8%, more preferably 0.05-0.5%, particularly
preferably 0.05-0.3%. In addition, (Sh-L / Sh//) and D(Sh± / Sh//) can
freely be controlled within the ranges of (Sh± / Sh//) = 1.6-2.4 and D(ShJ_ /
Sh//) = 0.05-0.30. To suppress dimensional variations of ferrite magnet
products, as the molar ratio n nears about 6, D(ShJ_ / Sh//) can be made
small, with (Sh_L / Sh//) controlled to 1.9-2.2. A(Sh± / Sh//) is controlled
to more preferably 0.05-0.20, further preferably 0.05-0.15, particularly
preferably 0.05-0.10.
EXAMPLE 8
SrCO3 and Fe2O3 were formulated to provide a basic composition of
SrO-nFe2O3, wherein n = 5.6, wet-mixed, and then calcined at 1250°C for 2
hours in the air. Thereafter, 2-8 weight % of Fe3O4 (magnetite) was added
at an early stage of the fine pulverization step of coarse powder by a post-
addition method in the same manner as in EXAMPLE 6, to produce sintered
ferrite magnets. Each of the resultant sintered bodies substantially had the
following composition:
(Sr1.xLax)O-n[(Fe1.yCo05yZn05y)2O3] by atomic ratio,
wherein x = 0.15, y = x/2n, and n = 5.00-5.34.
Among them, ferrite magnets having n of 5.00-5.20 had
substantially as high magnetic properties as those of EXAMPLE 7, fully
satisfactory for practical applications. Also, the ferrite magnets having n
exceeding 5.20 had substantially the same magnetic properties as those of
the equimolar-ratio ferrite magnets obtained in EXAMPLE 6.
EXAMPLE 9
A ferrite magnet was produced in the same manner as in EXAMPLE
8 except for adding no Fe3O4 (magnetite) at an early stage of the fine
pulverization step of coarse powder, to measure magnetic properties
thereof. The resultant ferrite magnet had a squareness ratio Hk/iHc of
93.5%.
EXAMPLE 10
SrCO3, Fe2O3, La2O3 and Co3O4 were formulated to provide a basic
composition represented by the following formula:
(Sr1.xLax)O-n[(Fe1.yCoy)2O3] by atomic ratio,
wherein x = 0.075, y = x/2n, and n = 5.9, wet-mixed, and then calcined at
1250°C for 2 hours in the air. The calcined powder was coarsely
pulverized in a dry state by a roller mill, and then finely pulverized in a wet
state by an attritor to produce a slurry containing fine powder of 0.8 mm in
average diameter. Added at an early stage of the fine pulverization of
each coarse powder were 1.25 weight % of La2O3 and 0.6 weight % of
Co3O4, together with 1-4 weight % of Fe3O4 (magnetite), based on the
weight of the coarse powder. Further, 0.1 weight % of SrCO3,1.0
weight % of CaCO3 and 0.3 weight % of SiO2, based on the weight of the
coarse powder, were added as sintering aids at an early stage of the fine
pulverization of coarse powder. The resultant fine powder slurry was
wet-molded in a magnetic field of 10 kOe, and each of the resultant green
bodies was sintered at 1210-1230°C for 2 hours. Each of the resultant
sintered bodies substantially had a basic composition corresponding to
(Sr1.xLax)O-n[(Fe1.yCoy)2O3] by atomic ratio,
wherein y = x/2n, x = 0.15, and n = 5.61-5.78.
Each of the resultant sintered bodies was machined to a shape of
about 10 mm x 10 mm x 20 mm to measure magnetic properties at 20° C by
a B-H tracer. It has been found that any ferrite magnets had substantially
as high magnetic properties as those of the equimolar-ratio ferrite magnets
shown in Fig 2.
EXAMPLE 11
A ferrite magnet was produced in the same manner as in EXAMPLE
10 except for adding no Fe3O4 (magnetite) at an early stage of the fine
pulverization step of coarse powder, to measure magnetic properties
thereof.
The comparison of EXAMPLES 10 and 11 indicated the tendency
that as the amount of Fe3O4 added increased, the magnetic properties were
gradually improved, and both A(Shl) and A(Shl / Sh//) decreased.
EXAMPLE 12
SrCO3, Fe2O3, La2O3, Co3O4 and ZnO were formulated to provide a
basic composition represented by the following formula:
(Sr1.xLax)O-n[(Fe1.yCo05yZn05y)2O3] by atomic ratio,
wherein x = 0.075, y = x/2n, and n = 5.9, wet-mixed, and then calcined at
1250°C for 2 hours in the air. The calcined powder was coarsely
pulverized in a dry state by a roller mill, and then finely pulverized in a wet
state by an attritor to produce a slurry containing fine powder of 0.8 mm in
average diameter. Added at an early stage of the fine pulverization of
each coarse powder were 1.25 weight % of La2O3, 0.3 weight % of Co3O4
and 0.3 weight % of ZnO, together with 1-4 weight % of Fe3O4 (magnetite),
based on the weight of the coarse powder. Further, 0.1 weight % of
SrCO3,1.0 weight % of CaCO3 and 0.3 weight % of SiO2, based on the
weight of the coarse powder, were added as sintering aids at an early stage
of the fine pulverization of coarse powder. The resultant fine powder
slurry was wet-molded in a magnetic field of 10 kOe, and each of the
resultant green bodies was sintered at 1210-1230°C for 2 hours. Each of
the resultant sintered bodies substantially had a basic composition
corresponding to
(Sr1.xLax)O-n[(Fe1.yCo05yZn05y)2O3] by atomic ratio,
wherein x = 0.15, y = x/2n, and n = 5.60-5.77.
Each of the resultant sintered bodies was machined to a shape of
about 10 mm x 10 mm x 20 mm to measure magnetic properties at 20°C by
a B-H tracer. It has been found that any ferrite magnets had substantially
as high magnetic properties as those of the equimolar-ratio ferrite magnets
shown in Fig 6, and that their A(Sh±) was stably less than 0.5%.
EXAMPLE 13
A ferrite magnet was produced in the same manner as in EXAMPLE
12 except for adding no Fe3O4 (magnetite) at an early stage of the fine
pulverization step of coarse powder, to measure magnetic properties
thereof at 20°C by a B-H tracer.
The comparison of EXAMPLES 12 and 13 indicated the tendency
that as the amount of Fe3O4 added increased, the magnetic properties were
gradually improved, and both A(Sh±) and A(Sh_L / Sh//) decreased.
By adding both La and Co, and by utilizing the post or prior/post-
addition method by which the molar ratio n can be freely controlled, it is
possible to provide high-coercivity, high-performance ferrite magnets
having Br of 4,400-4,500 G, iHc of 4,400-4,500 Oe and Hk/iHc of 95-96%
at 20°C, when compositions are selected to meet 0.1^x By adding Cr2O3 and/or A12O3 remarkably increasing iHc while
decreasing Br in an amount of 0.1-2 weight %, more preferably 0.2-1.5
weight %, particularly preferably 0.3-1.0 weight %, it is possible to provide
high-performance ferrite magnets having higher coercivity than that of
conventional ferrite magnets while keeping high Br. When the amount of
Cr2O3 and/or A12O3 added is less than 0.1 weight %, effects of adding such
component are not appreciated. On the other hand, when it exceeds 2
weight %, Br drastically decreases. For instance, when 0.3-1.0 weight %
of Cr2O3 and/or A12O3 is added to the ferrite magnets of the present
invention, they can be turned to high-performance ferrite magnets having
extremely high coercivity, specifically Br of 4,200-4,300 G and iHc of
4,800-5,200 Oe at 20°C.
By adding La, Co and Zn and/or Mn, and by utilizing the post or
prior/post-addition method by which the molar ratio n can be freely
controlled according to the present invention, it is possible to provide high-
Br, high-performance ferrite magnets having Br of 4,400-4,600 G, iHc of
3,300-3,800 Oe and Hk/iHc of 95-97% at 20°C.
In the above EXAMPLES utilizing the post-addition method and/or
the prior/post-addition method, the Fe compounds such as magnetite or
hematite were post-added at the time of fine pulverization. However, it
should be noted that the timing of the post-addition of the Fe compounds is
not particularly restricted, as long as it is after calcination. The post-
addition of the Fe compounds can be carried out at any time between a
state of calcined powder obtained by completion of a ferritization reaction
and molding. When the post-addition of the Fe compounds is carried out
at a time outside the fine pulverization step, it is preferable to perform
uniform mixing such as mixing with agitation. When compounds of the R
elements and/or the M elements are post-added, their post-addition can be
carried out at any time between a state of calcined powder obtained by
completion of a ferritization reaction and molding.
Next, it has been found that if compounds of rare earth elements are
added not in the form of oxides but in the form of hydroxides, carbonates
or organic acid salts in the production of the ferrite magnets of the present
invention, reactivity would be improved, resulting in increase in the
magnetic properties of the resultant ferrite magnets. The first factor for
achieving improvement in the magnetic properties is that the hydroxides,
carbonates or organic acid salts of the R elements such as La, etc. are in the
form of finer powder than R element oxides. The second factor is that
when the hydroxides, carbonates or organic acid salts of the rare earth
elements are decomposed to oxides in a temperature elevation stage at
calcination or sintering, primary crystal grains are made finer, resulting in
increase in reactivity. The third factor is that the above decomposition
reaction per se contributes to increase in reactivity. It appears that these
first to third factors similarly exist in the case of hydroxides, etc. of the M
elements such as Co, etc.
One example suitable for mass production is that hydroxides, etc. of
the R element and the M element are added at the time of pulverization
(particularly fine pulverization) after calcination to provide the final
composition of the ferrite magnet according to the present invention.
Effects of improving magnetic properties by hydroxides, etc. of the R
elements and/or the M elements are remarkable particularly in the case of
the post-addition method. This is because a ferrite composition undergoes
only one high-temperature process, particularly a sintering process, in the
post-addition method, whereby high reactivity of hydroxides, carbonates or
organic acid salts is much more effective than in the case of a post-addition
method using oxides.
As an applied example in which a hydroxide of the M element is
post-added, the direct addition of the hydroxide powder may be changed to
the addition of a hydroxide of the M element formed by mixing a
dispersion of ferrite material powder in a CoCl2 aqueous solution with an
alkaline material such as NaOH, NH4OH, etc. The same is true of La.
EXAMPLE 14
SrCO3 and Fe2O3 were formulated to provide a basic composition of
SrO5.9Fe203, wet-mixed, and then calcined at 1200°C for 2 hours in the
air. The calcined powder was coarsely pulverized in a dry state by a roller
mill, and then finely pulverized in a wet state by an attritor to produce a
slurry containing fine powder of 0.7-0.8 \xm in average diameter.
La(OH)3 and Co(OH)2 were added at an early stage of the fine
pulverization of coarse powder. Further, 0.50 weight % of SrCO3, 0.80
weight % of CaCO3 and 0.45 weight % of SiO2, based on the weight of the
coarse powder, were added as sintering aids. The resultant fine powder
slurry was wet-molded in a magnetic field of 10 kOe, and each of the
resultant green bodies was sintered at 1210-1230°C for 2 hours. Each of
the resultant sintered bodies substantially had the following formula:
(SrlxLax)On[(Fei.yCoy)2O3],
wherein x = 0.15, y = x/2n, and n = 5.20.
Each of the resultant sintered bodies was machined to a shape of
about 10 mm x 10 mm x 20 mm to measure magnetic properties at 20° C by
a B-H tracer. The results are shown in Table 3.
COMPARATIVE EXAMPLE 6
A ferrite magnet was produced in the same manner as in EXAMPLE
A t-l jf
14 except for adding La2O3 and Co3O4 in such amounts as to meet x = 0.15
at a mixing step before calcination, to measure magnetic properties thereof.
The results are shown in Table 3.
EXAMPLE 15
A ferrite magnet was produced in the same manner as in EXAMPLE
14 except for adding La2O3 and Co3O4 in such amounts as to meet x = 0.15
and y = x/2n at an early stage of the fine pulverization step of coarse
powder, to measure magnetic properties thereof at 20°C by a B-H tracer.
The results are shown in Table 3.
20° C. It is considered that the value of Hk/iHc is a measure representing
not only a squareness ratio of a demagnetization curve, but also the
effectiveness of a La element and a Co element substituted to A ion sites
and Fe ion sites in the M-type ferrite sintered body.
The comparison of EXAMPLES 14 and 15 and COMPARATIVE
EXAMPLE 6 in Table 3 indicated that by adding the La compound and the
Co compound at the time of fine pulverization, and by using La(OH)3 and
Co(OH)2 as the La compound and the Co compound, iHc could be
remarkably improved while keeping the squareness ratio Hk/iHc at a good
level.
EXAMPLE 16
A calcined powder having a basic composition of SrO-6.0Fe2O3 was
produced by calcination at 1200°C for 2 hours in the air. The calcined
powder was coarsely pulverized in a dry state by a roller mill, and then
finely pulverized in a wet state by an attritor to produce a slurry containing
fine powder of 0.8 \xm in average diameter. Co3O4, ZnO and La(OH)3
were added in such amounts as to have a basic composition represented by
(Sr1.xLax)O-n[(Fe1.yCo05yZn05y)2O3], wherein x = 0.15, y = x/2n, and n = 5.3,
at an early stage of the fine pulverization of coarse powder. Also, 0.50
weight % of SrCO3, 0.40 weight % of SiO2 and 0.80% weight of CaCO3
(0.45 weight % as CaO), based on the weight of the coarse powder, were
added as sintering aids at an early stage of the fine pulverization of coarse
powder. The resultant fine powder slurry was wet-molded in a magnetic
field of 10 kOe, and each of the resultant green bodies was sintered at
1210-1230°C for 2 hours. Each of the resultant sintered bodies was
machined to a shape of about 10 mm x 10 mm x 20 mm to measure
magnetic properties at 20°C by a B-H tracer. The results are shown in
Table 4.
EXAMPLE 17
A ferrite magnet was produced in the same manner as in EXAMPLE
16 except for adding La2O3 in place of La(OH)3 at the time of fine
pulverization, to measure magnetic properties thereof at 20°C by a B-H
tracer. The results are shown in Table 4.
COMPARATIVE EXAMPLE 7
A ferrite magnet was produced in the same manner as in EXAMPLE
16 except for adding La2O3 in place of La(OH)3 at the time of mixing
before calcination, to measure magnetic properties thereof. The results
are shown in Table 4.
The comparison of EXAMPLES 16 and 17 and COMPARATIVE
EXAMPLE 7 in Table 4 indicated that the post-addition of La, Co and Zn
served to improve Hk/iHc. It is also clear that La(OH)3 is effective in the
case of adding La, Co and Zn.
EXAMPLE 18
SrCO3, Fe2O3, La2O3 and Co3O4 were formulated to provide a basic
composition represented by the following formula:
(Sr1-xLx)O-n(Fe1-yCoy)2O3],
wherein x = 0.075, y = x/2n, and n = 5.9, wet-mixed, and then calcined at
1200°C for 2 hours in the air. The calcined powder was coarsely
pulverized in a dry state by a roller mill, and then finely pulverized in a wet
state by an attritor to produce a slurry containing fine powder of 0.7-0.8 mm
in average diameter. Post-added at an early stage of the fine pulverization
of each coarse powder were La2O3 and Co3O4 in such amounts as to meet x
= 0.15, y = x/2n, and n = 5.55. Further, 0.50 weight % of SrCO3, 0.80
weight % of CaCO3 and 0.45 weight % of SiO2, based on the weight of the
coarse powder, were added as sintering aids at an early stage of the fine
pulverization of coarse powder. The resultant fine powder slurry was
wet-molded in a magnetic field of 10 kOe, and each of the resultant green
bodies was sintered at 1210-1230°C for 2 hours. Each of the resultant
sintered bodies was machined to a shape of about 10 mm x 10 mm x 20
mm to measure magnetic properties at 20°C by a B-H tracer. The results
are shown in Table 5.
EXAMPLE 19
SrCO3, Fe2O3, La(OH)3 and Co3O4 were formulated to provide a
basic composition represented by the following formula:
(Sr1.xLax)O-n[(Fe1.yCoy)2O3] by atomic ratio,
wherein x = 0.075, y = x/2n, and n = 5.9, wet-mixed, and then calcined at
1200°C for 2 hours in the air. The calcined powder was coarsely
pulverized in a dry state by a roller mill, and then finely pulverized in a wet
state by an attritor to produce a slurry containing fine powder of 0.7-0.8 mm
in average diameter. Post-added at an early stage of the fine pulverization
of each coarse powder were La(OH)3 and Co3O4 in such amounts as to
meet x = 0.15, y = x/2n, and n = 5.55. Further, 0.50 weight % of SrCO3,
0.80 weight % of CaCO3 and 0.45 weight % of SiO2, based on the weight
of the coarse powder, were added as sintering aids at an early stage of the
fine pulverization of coarse powder. The resultant fine powder slurry was
wet-molded in a magnetic field of 10 kOe, and each of the resultant green
bodies was sintered at 1210-1230°C for 2 hours. Each of the resultant
sintered bodies was machined to a shape of about 10 mm x 10 mm x 20
mm to measure magnetic properties at 20° C by a B-H tracer. The results
are shown in Table 5.
EXAMPLE 20
SrCO3, Fe2O3, Co3O4, ZnO and La2O3 were formulated to provide a
basic composition represented by the following formula:
(Sr1.xLax)O-n[(Fe1.yCo0 5yZn0.5y)2O3] by atomic ratio,
wherein x = 0.075, y = x/2n, and n = 6.0, wet-mixed, and then calcined at
1200°C for 2 hours in the air. The calcined powder was coarsely
pulverized in a dry state by a roller mill, and then finely pulverized in a wet
state by an attritor to produce a slurry containing fine powder of 0.8 mm in
average diameter. Post-added at an early stage of the fine pulverization of
each coarse powder were La2O3, Co3O4 and ZnO in such amounts as to
meet x = 0.15, y = x/2n, and n = 5.65. Further, 0.50 weight % of SrCO3,
0.40 weight % of SiO2 and 0.80 weight % of CaCO3 (0.45 weight % as
CaO), based on the weight of the coarse powder, were added as sintering
aids at an early stage of the fine pulverization of coarse powder. The
resultant fine powder slurry was wet-molded in a magnetic field of 10 kOe,
and each of the resultant green bodies was sintered at 1210-1230°C for 2
hours. Each of the resultant sintered bodies was machined to a shape of
about 10 mm x 10 mm x 20 mm to measure magnetic properties at 20°C by
a B-H tracer. The results are shown in Table 6.
EXAMPLE 21
SrCO3, Fe2O3, Co3O4, ZnO and La(OH)3 were formulated to provide
a basic composition represented by the following formula:
(Sr1.xLax)O-n[(Fe1.yCo05yZn05y)2O3] by atomic ratio,
wherein x = 0.075, y = x/2n, and n = 6.0, wet-mixed, and then calcined at
1200°C for 2 hours in the air. The calcined powder was coarsely
pulverized in a dry state by a roller mill, and then finely pulverized in a wet
state by an attritor to produce a slurry containing fine powder of 0.8 mm in
average diameter. Post-added at an early stage of the fine pulverization of
each coarse powder were La(OH)3, Co3O4 and ZnO in such amounts as to
meet x = 0.15, y = x/2n, and n = 5.65. Further, 0.50 weight % of SrCO3,
0.40 weight % of SiO2 and 0.80 weight % of CaCO3 (0.45 weight % as
CaO), based on the weight of the coarse powder, were added as sintering
aids at an early stage of the fine pulverization of coarse powder. The
resultant fine powder slurry was wet-molded in a magnetic field of 10 kOe,
and each of the resultant green bodies was sintered at 1210-1230°C for 2
hours. Each of the resultant sintered bodies was machined to a shape of
about 10 mm x 10 mm x 20 mm to measure magnetic properties at 20°C by
a B-H tracer. The results are shown in Table 6.
EXAMPLE 22
To measure the temperature characteristics of the ferrite magnets of
the present invention, ferrite magnets produced at x = 0.15 (EXAMPLE 18)
were machined to a predetermined shape as samples. Also, ferrite
magnets were produced in the same manner as in EXAMPLE 18 except for
changing x to 0, 0.10 and 0.20, respectively, and likewise machined to a
predetermined shape as samples. Each sample was set in a vibration-type
magnetometer (VSM-3, available from Toei Kogyo K.K.) to measure
magnetic properties at temperatures varying every 10°C from -60° C to
+100°C, thereby determining a temperature coefficient (a) of Br and a
temperature coefficient (p) of iHc at -60°C to +100°C. The results are
shown in Table 7.
Table 7
x a (%/°C) p (%/°C)
0 -0.190 0.378
0.10 -0.191 0.254
0.15 -0.192 0.196
0.20 -0.191 0.132
It has been found from investigation in connection with the data of
Table 7 that the ferrite magnets of the present invention obtained by
addition of La and Co have p ranging from 0.13 %/°C to 0.36 %/°C. Also,
related investigation has revealed that the ferrite magnets of the present
invention as shown in Table 7 have Curie temperatures (Tc) in a range of
425°C EXAMPLE 23
To measure the temperature characteristics of the ferrite magnets of
the present invention obtained by addition of La, Co and Zn, ferrite
magnets of EXAMPLE 20 (x = 0.15) were machined to a predetermined
shape as samples. Each sample was measured with respect to magnetic
properties at-60°C to +100°C in the same manner as in EXAMPLE 22,
thereby determining a temperature coefficient (a) of Br and a temperature
coefficient (b) of iHc. The results are shown in Table 8.
The data of Table 8 have revealed that the ferrite magnets of the
present invention obtained by addition of La, Co and Zn have b ranging
from 0.26 %/°C to 0.36 %/°C.
Fig. 7 shows the EPMA analysis results of the ferrite magnets of
COMPARATIVE EXAMPLE 4 (prior-addition method, x = 0.15, and n =
5.85). Fig. 8 shows the EPMA analysis results of the ferrite magnets of
EXAMPLE 1 (post-addition method, x = 0.15, n = 5.25, and Fe3O4 = 0
weight %). Fig. 9 shows the EPMA analysis results of the ferrite magnets
of EXAMPLE 2 (post-addition method, x = 0.15, n = 5.55, and Fe3O4 = 6
weight %). Fig. 10 shows the EPMA analysis results of the ferrite
magnets (prior/post-addition method, x = 0.20, n = 5.90, and Fe3O4 = 6
weight %) produced in the same manner as in EXAMPLE 10 except for
preparing calcined powder having a basic composition of
(Sr1.xLax)O-n[(Fe1.yCoy)2O3], wherein x = 0.10, y = x/2n, and n = 6.0, and
adding predetermined amounts of La2O3, Co3O4 and Fe3O4 at the time of
fine pulverization.
Each sample for EPMA analysis as shown in Figs. 7-10 was
embedded in a resin such that a c surface of the ferrite magnet appeared on
a surface of the resin, and mirror-polished for EPMA line analysis with
A12O3 abrasive powder having a particle size of 0.05 mm. Used as an
EPMA apparatus was an electron probe micro-analyzer (EPM-810Q,
available from Shimadzu Corp.). The measurement conditions were an
acceleration voltage of 15 kV, an acceleration current of 0.1 mA, and an
irradiation beam diameter of 1 mm. In Figs. 7-10, the axis of ordinates
represents the counts per second (c.p.s.) of each element of La, Co, Sr and
Fe, and the axis of abscissas represents a scanning distance (mm). Figs. 7-
10 show scales for the c.p.s. and the scanning distance. Spectroscopic
crystals used in the EPMA apparatus were lithium fluoride (LiF) for the
line analysis of La, pentaerythritol [PET, C(CH2OH)4] for the line analysis
of Sr, rubidium acidic phthalate [(RAP, C6H4(COOH)(COORb)] for the line
analysis of Fe, and LiF for the line analysis of Co.
As shown in Figs. 7-10, variations of the c.p.s. of La read on the
EPMA results in an arbitrary 80-mm range on a surface of each sample was
defined as A(c.p.s.). In Fig. 7 (prior-addition method, x = 0.15, and n =
5.85), A(c.p.s.) = 0.119 kc.p.s. In Fig. 8 (post-addition method, x = 0.15,
n = 5.25, and Fe3O4 = 0 weight %), A(c.p.s.) = 0.512 kc.p.s. In Fig. 9
(post-addition method, x = 0.15, n = 5.55, and Fe3O4 = 6
weight %), A(c.p.s.) = 0.557 kc.p.s. In Fig. 10 (prior/post-addition
method, x = 0.20, n = 5.90, and Fe3O4 = 6 weight %), A(c.p.s.) = 0.252
kc.p.s.
It is clear from investigation in connection with Fig. 7 that the prior-
addition method provides D(c.p.s.) = 0.07-0.15 kc.p.s., suggesting that La is
distributed more uniformly by the prior-addition method than the post-
addition method in Figs. 8 and 9 and the prior/post-addition method in Fig.
10. The investigation of Figs. 8 and 9 has revealed that the post-addition
method provides A(c.p.s.) = 0.35-0.65, suggesting that the distribution of
La is the most non-uniform. Further, Figs. 8 and 9 have revealed the
tendency that the addition of Fe3O4 slightly contributes to increase in
A(c.p.s.). Next, Fig. 10 has revealed that in the prior/post-addition method
in which the contribution of the post-addition to the value of x and/or y is
20% or more and less than 100%, D(c.p.s.) is 0.15-0.35, suggesting that the
distribution of La is between that of the post-addition method and that of
the prior/post-addition method.
Fig. 11 shows the magnetization-temperature curves of the ferrite
magnets produced by the prior-addition method, each of which has a basic
composition represented by (Sr1.xLax)O-n[(Fe1.yCoy)2O3] by atomic ratio,
wherein x = 0.10-0.40, y = x/2n, and n = 5.9. The axis of ordinates
represents magnetization (relative value), x = 0 represents a ferrite
magnet having a conventional composition of SrO5.9Fe203.
An intersection of a tangent (broken line) of each curve and the axis of
abscissas (magnetization = 0) is defined as the first Curie temperature (Tc1),
and an intersection of each curve and the axis of abscissas (magnetization =
0) is defined as the second Curie temperature (Tc2). Fig. 11 shows that in
the magnetization-temperature curves of the ferrite magnets of x = 0-0.40
produced by the prior-addition method, curve portions encircled by O are
convexly curved relative to the tangent (broken line) extending through Tc1
Fig. 12 shows magnetization-temperature curves obtained by
measurement of samples cut away from the same ferrite magnets as in Fig.
9 (post-addition method, x = 0.15, n = 5.55, and Fe3O4 = 6 weight %). Fig.
12 further shows magnetization-temperature curves obtained by
measurement of samples cut away from the same ferrite magnets as in Fig.
10 (prior/post-addition method, x = 0.20, n = 5.90, and Fe3O4 = 6
weight %). In the case of those obtained by the post-addition method
shown in Fig. 12,Tc1 = 447°C, and Tc2 = 453°C, curve portions encircled
by O being concavely curved relative to the tangent (broken line)
extending through Tc1. In the case of those obtained by the prior/post-
addition method shown in Fig. 12, Tcx = 445°C, and Tc2 = 453°C, curve
portions encircled by O being concavely curved relative to the tangent
(broken line) extending through Tc1
EXAMPLE 24
A ferrite magnet having the following basic composition:
(Sr1.xLax)O-n[(Fe1.yCoy)2O3] by atomic ratio,
wherein x = 0.15, y = x/2n, and n = 5.55, was produced by a post-addition
method in the same manner as in EXAMPLE 2 except for using calcined
powder having a basic composition of SrO-5.9Fe2P3, adjusting an average
diameter of fine powder to 0.65 mm, and adding 7 weight % of Fe3O4 at the
time of fine pulverization. 4pI-H curves of this ferrite magnet at 20° C
and -40°C, respectively, are shown in Fig. 13. By utilizing the post-
addition method with a desired amount of Fe3O4 added, and adjusting the
average diameter of fine powder to a level of 0.4-0.65 mm suitable for high
Br, extremely high Br, iHc and squareness ratio Hk/iHc, specifically Br of
4.4 kG, iHc of 4.5 kOe and a squareness ratio Hk/iHc of 95% at 20°C, have
been realized.
The measurement results of a critical demagnetizing field intensity
(AH) of this high-performance ferrite magnet at -40°C will be explained
below. In Fig. 13, an operation line pi determined by a magnetic circuit
comprising a ferrite magnet has an operation point at a point A on the B-H
curve, and the operation point A corresponds to a point Q on the 4peI-H
curve. By measurements under the condition of pi = pc +1 = 3, wherein
pi represents a permeance coefficient on the 4pI-H curve, and pc represents
a permeance coefficient on the B-H curve, AH was 2240 Oe as shown in
Fig. 13. pi' is an operation line parallel with the operation line pi. Under
the conditions of —40°C, and pi = pc +1 = 3, a magnetic flux density at the
operation point A before application of AH is Bdr When AH of 2240 Oe
is applied, the operation point moves to a point D on the B-H curve
corresponding to the intersection C of the operation line pi1 and the 4jiI-H
curve. After removal of a demagnetizing field, the operation point
substantially returns to the point A at DH = 0. Thus, the magnetic flux
density (Bdt) = 3650 G at the point A before application of AH is
substantially equal to the magnetic flux density (Bd2) at the operation point
after application and removal of DH, which returns to the point A.
Accordingly, the irreversible loss of magnetic flux defined by [(Bd1 - Bd2)
/ Bd1] x 100% is substantially 0%.
COMPARATIVE EXAMPLE 8
A ferrite magnet was produced in the same manner as in
COMPARATIVE EXAMPLE 4 except for formulating starting materials by a
prior-addition method to have the following basic composition:
(Sr1.xLax)O'n[(Fe1.yCoy)2O3] by atomic ratio,
wherein x = 0.15, y = x/2n, and n = 5.85. 4pI-H curves of this ferrite
magnet at +20°C and -40°C, respectively, are shown in Fig. 14. Because
this ferrite magnet was produced by the prior-addition method, a
squareness ratio Hk/iHc was as low as 76% at 20°C, though Br and iHc
were as high as 4.4 kG and 4.5 kOe, respectively, at 20°C.
Fig. 14 shows the measurement results of a critical demagnetizing
field intensity (AH') of this ferrite magnet with a poor squareness ratio in
the same manner as in Fig. 13 at -40°C. In Fig. 14, an operation line pi
determined by a magnetic circuit comprising a ferrite magnet has an
operation point at a point H on the B-H curve, and the operation point H
corresponds to a point K on the 4jiI-H curve, pi' and pi" are operation
lines parallel with the operation line pi. As shown in Fig. 14, a critical
magnetic field intensity (AH') at which demagnetization does not take
place under the conditions of -40°C and pi = 3 is 560 Oe (25% relative to
AH in Fig. 13).
Next, an irreversible loss of magnetic flux was measured after
application and removal of a demagnetizing field of 2240 Oe in the same
manner as in Fig 13. When the demagnetizing field of 2240 Oe is applied
under the conditions of-40°C and pi = 3, the operation point moves to a
point G on the B-H curve corresponding to the intersection F of the
operation line pi' and the 4jiI-H curve. After removal of a demagnetizing
field of 2240 Oe, the operation point substantially returns to the point H', at
which the magnetic flux density (Bd2') is 3240 G. Since the magnetic
flux density (Bdj') at the operation point H is 3640G before application of
the demagnetizing field of 2240 Oe, the irreversible loss of magnetic flux is
[(3640-3240) / 3640] x 100% = 11.0%, suggesting a larger loss of
magnetic flux than in Fig 13.
Investigation of Figs. 13 and 14 has revealed that in the case of the
ferrite magnet of the present invention (R = La, and M = Co) having Br of
4100 G or more, iHc of 4000 Oe or more and Hk/iHc of 92.3% or more,
AH may be preferably 1000 Oe or more, more preferably 1500 Oe or more,
particularly preferably 2000 Oe or more under the conditions of-40°C and
pi^3. This ferrite magnet is suitable for solid, cylindrical magnets or ring-
shaped magnets with radial or polar anisotropy capable of being
magnetized symmetrically or unsymmetrically with 4-24 magnetic poles,
more preferably 4-16 magnetic poles. The solid, cylindrical magnet or the
ring-shaped magnet may be constituted by an integral ferrite magnet or a
plurality of ferrite magnet pieces bonded together. Such integral or
combined ferrite magnets can constitute, for instance, long magnet rolls for
photocopiers. The present invention greatly contributes to improvement
in performance and miniaturization of rotors, photocopiers, etc.
In the ferrite magnet of the present invention (R = La, and M = Co
+ Zn and/or Mn) having Br of 4200 G or more, iHc of 3000 Oe or more
and Hk/iHc of 93.5% or more at 20°C, too, AH can be greatly improved
with irreversible loss of magnetic flux suppressed.
Though the above EXAMPLES are related to Sr ferrite whose R and
M elements are substituted, it should be noted that Ba ferrite and Sr-Ba
ferrite, whose R and M elements are substituted, also substantially have a
magnetoplumbite-type crystal structure showing higher coercivity iHc (or
higher coercivity iHc and residual magnetic flux density Br) than those of
conventional ferrite magnets.
Compounds effective for improving magnetic properties such as
B2O3, Bi compounds, etc., other than SiO2 and CaO, may be added to the
ferrite magnet of the present invention having a magnetoplumbite-type
crystal structure. Also, the ferrite magnet of the present invention may
contain less than predetermined amounts of inevitable impurities, in
addition to the above indispensable components.
APPLICATIONS IN INDUSTRY
Because the ferrite magnet of the present invention is produced by
the post-addition method and/or the prior/post-addition method in which
the molar ratio n can freely be controlled, not only has it a microstructure in
which the concentrations of rare earth elements are high in crystal grain
boundaries, but also is it easily mass-produced. Thus, the ferrite magnet
of the present invention has higher coercivity iHc (or higher coercivity iHc
and residual magnetic flux density Br), higher squareness ratio Hk/iHc and
smaller variation of a shrinkage ratio than those of conventional ferrite
magnets.
The ferrite magnets having such characteristics according to the
present invention are extremely useful for various rotors, actuators, etc.
required to have high Br and iHc. The Co content of less than 10
atomic % extremely reduces iHc, while the Co content exceeding 95.
atomic % substantially nullifies the effects of adding Zn.
The ferrite magnet according to one embodiment of the present
invention has higher iHc than that of conventional ferrite magnets, while
keeping Br equal to or higher than that of the conventional ferrite magnets.
Therefore, such ferrite magnet of the present invention is expected to be
used for motors for ABS, starters, etc.
The ferrite magnet according to another embodiment of the present
invention has higher Br than that of conventional ferrite magnets, while
keeping iHc equal to or higher than that of the conventional ferrite magnets.
Therefore, such ferrite magnet of the present invention is expected to be
used for motors for compressors of air conditioners, etc.
WE CLAIM:
1. A method for producing an anisotropic, sintered ferrite magnet
having a basic composition represented by the following general formula:
(A1-xRx)O.n[ (Fe1-yMy)2O3] by atomic ratio,
wherein A is Sr or (Sr+Ba), and Sr is an indispensable element, R
is at least one of rare earth elements including Y, M is at least one
element selected from the group consisting of Co, Mn, Ni and Zn, and Co
is an indispensable element, and the percentage of Co in M is 50 atomic
% or more, and x, y and n are numbers meeting the following conditions:
0.01 =x=0.4,
0.005 =y=0.04, and
5=n=6
said anisotropic, sintered ferrite magnet having a
magnetoplumbite-type crystal structure,
said method comprising the steps of uniformly mixing at least one
of Sr compound and Ba compound with Fe compound; calcining the
resultant uniform mixture; adding the R element and the M element in
the form of a compound to the resultant calcined powder at a
pulverization step after the calcination thereof; molding the resultant
pulverized powder in a in a magnetic field; and sintering the
resultant green body, wherein a hydroxide of the R element is added as
said R compound, and/or a hydroxide of the M element is added as said
M compound.
2. The method for producing an anisotropic, sintered ferrite magnet
as claimed in claim 1, wherein said M element is Co.
3. The method of producing an anisotropic, sintered ferrite magnet as
claimed in claim 1, wherein Fe compound is further added at the
pulverization step after the calcination.
4. The method of producing an anisotropic, sintered ferrite magnet as
claimed in claim 1, wherein an average diameter of said pulverized
powder is 0.7 um or more.
5. A method for producing an anisotropic, sintered ferrite magnet
substantially as herein described with reference to and as illustrated in
the accompanying drawings.
A ferrite magnet having a basic composition represented by the following
general formula: (A1-xRx)O-n[(Fe1-yMy)2O3] by atomic ratio, wherein A is Sr
and/or Ba, R is at least one of rare earth elements including Y, M is at least
one element selected from the group consisting of Co, Mn, Ni and Zn, and
x, y and n are numbers meeting the conditions of 0.01=x=0.4,
[x/(2.6n)]=y=[x/(1.6n)], and 5=n=6, and substantially having a
magnetoplumbite-type crystal structure, is obtained by uniformly mixing a
compound of Sr and/or Ba with an iron compound; calcining the resultant
uniform mixture; adding a compound of the R element and/or the M
element to the resultant calcined powder at a pulverization step thereof; and
sintering the resultant mixture. The compound of the R element and/or
the M element may be added at a percentage of more than 0 atomic % and
80 atomic % or less, on an element basis, at a mixing step before
calcination.

Documents:

IN-PCT-1999-26-KOL-FORM-27.pdf

in-pct-1999-26-kol-granted-abstract.pdf

in-pct-1999-26-kol-granted-claims.pdf

in-pct-1999-26-kol-granted-correspondence.pdf

in-pct-1999-26-kol-granted-description (complete).pdf

in-pct-1999-26-kol-granted-drawings.pdf

in-pct-1999-26-kol-granted-examination report.pdf

in-pct-1999-26-kol-granted-form 1.pdf

in-pct-1999-26-kol-granted-form 18.pdf

in-pct-1999-26-kol-granted-form 2.pdf

in-pct-1999-26-kol-granted-form 3.pdf

in-pct-1999-26-kol-granted-form 5.pdf

in-pct-1999-26-kol-granted-form 6.pdf

in-pct-1999-26-kol-granted-pa.pdf

in-pct-1999-26-kol-granted-priority document.pdf

in-pct-1999-26-kol-granted-reply to examination report.pdf

in-pct-1999-26-kol-granted-specification.pdf

in-pct-1999-26-kol-granted-translated copy of priority document.pdf


Patent Number 225655
Indian Patent Application Number IN/PCT/1999/26/KOL
PG Journal Number 47/2008
Publication Date 21-Nov-2008
Grant Date 19-Nov-2008
Date of Filing 31-Aug-1999
Name of Patentee HITACHI METALS., LTD.
Applicant Address 2-1, SHIBAURA 1-CHOME, MINATO-KU
Inventors:
# Inventor's Name Inventor's Address
1 TAKASHI TAKAMI 450, NIBORT-SHINDEN, KUMAGAYA-CHI, SAITAMA-KEN
2 YUTAKA KUBOTA 450, NIBORI-SHINDEN, KUMAGAYA-SHI, SAITAMA-KEN
3 YASUNOBU OGATA 5-14, KAMISHIBACHO-NISHI 4-CHOME, HUKAYA-SHI SAITAMA KEN
PCT International Classification Number H01F 1/11
PCT International Application Number PCT/JP98/05970
PCT International Filing date 1998-12-25
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 10-73998 1998-03-23 Japan
2 10-332498 1998-11-24 Japan
3 9-358552 1997-12-25 Japan
4 10-193662 1998-06-24 Japan
5 10-318466 1998-11-10 Japan