# Patent

## Title
Calcined ferrite, and sintered ferrite magnet and its production method

## Abstract

A sintered ferrite magnet having a composition of metal elements of Ca, R, A, Fe and Co, which is represented by the general formula of Ca1−x−yRxAyFe2n−zCoz, wherein R is at least one of rare earth elements indispensably including La; A is Sr and/or Ba; x, y, z and n represent the atomic ratios of Ca, R, A, Fe and Co; 2n represents a molar ratio expressed by 2n=(Fe+Co)/(Ca+R+A); and x, y, z and n meet the conditions of 0.15≤x≤0.35, 0.05≤y≤0.40, (1−x−y)>y, 0<z≤0.18, and 7.5≤(2n−z)<11.0.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This is a divisional of application Ser. No. 17/171,036 filed Feb. 9, 2021, which claims priority from Japanese Patent Application Nos. 2020-051978 filed Mar. 24, 2020, 2020-156832 filed Sep. 18, 2020, and 2020-215957 filed Dec. 25, 2020; the disclosure of application Ser. No. 17/171,036 is hereby incorporated by reference.


FIELD OF THE INVENTION
The present invention relates to a sintered ferrite magnet having an adjusted composition of metal elements of Ca, R, A, Fe and Co for exhibiting high magnetic properties even with a smaller Co content than those in conventional SrLaCo magnets and CaLaCo magnets, and its production method, and calcined ferrite for providing such a sintered ferrite magnet.
BACKGROUND OF THE INVENTION
Sintered ferrite magnets have excellent cost performance and extremely high chemical stability because their main raw material is inexpensive iron oxide, despite that their maximum energy products are only 1/10 of those of sintered rare earth magnets (for example, sintered NdFeB magnets). Accordingly, they are used for various applications such as motors, speakers, etc., and they are globally produced in largest weights among all magnet materials at present.
A typical sintered ferrite magnet is Sr ferrite having a magnetoplumbite structure, whose basic composition is represented by SrFe12O19. In late 1990s, sintered Sr—La—Co ferrite magnets having drastically improved magnetic properties by substituting part of Sr2+ with La3+ and part of Fe3+ with Co2+ in SrFe12O19, which may be called “SrLaCo magnets” for short below, were put into practical use. Also, in 2007, sintered Ca—La—Co ferrite magnets having further improved magnetic properties, which may be called “CaLaCo magnets” for short below, were put into practical use.
In both SrLaCo magnets and CaLaCo magnets described above, Co is indispensable to obtain high magnetic properties. SrLaCo magnets contain Co at atomic ratios of about 0.2 (Co/Fe=0.017, about 1.7% of the Fe content), and CaLaCo magnets contain Co at atomic ratios of as high as about 0.3 (Co/Fe=0.03, about 3% of the Fe content). Because cobalt oxide as a raw material of Co is ten to several tens of times as expensive as iron oxide, a main raw material of sintered ferrite magnets, CaLaCo magnets inevitably suffer higher material cost than SrLaCo magnets. Accordingly, more SrLaCo magnets with lower material cost are used than CaLaCo magnets at present, though CaLaCo magnets have higher magnetic properties.
As demand for Li ion batteries is increasing due to increase in electric vehicles, the price of Co is rapidly increasing in recent years. Due to such tendency, even SrLaCo magnets having excellent cost performance face difficulty in keeping their prices low. In such circumstances, it is imperative to reduce the use of Co in ferrite magnets while keeping their magnetic properties.
As a sintered Ca—La—Co ferrite magnet with a reduced Co content, WO 2008/105449 A discloses a sintered ferrite magnet having a ferrite phase having a hexagonal crystal structure as a main phase, the composition of metal elements constituting the main phase being represented by the general formula of RxCamA1−x−m(Fe12−yMy)z, wherein R is at least one element selected from the group consisting of La, Ce, Pr, Nd and Sm, including La as an indispensable component; A is Sr and/or Ba; M is at least one element selected from the group consisting of Co, Zn, Ni, Mn, Al and Cr, including Co as an indispensable component; and x, m, y and z meet 0.2≤x≤0.5, 0.13≤m≤0.41, 0.7(x−m)≤0.15, 0.18≤yz≤0.31, and 9.6≤12z≤11.8, respectively. In the above general formula, the Co content is 0.18-0.31 by atomic ratio.
However, in Examples of WO 2008/105449 A, the percentage of Sr to (Ca+La+Sr) is more than 0.5 by atomic ratio when the Co content is as small as 0.18 by atomic ratio, the Sr content being higher than the Ca content. Namely, in a region having a small Co content, the sintered ferrite magnets of WO 2008/105449 A have compositions close to those of Sr—La—Co-based, sintered ferrite magnets, indicating that WO 2008/105449 A does not describe examples of Ca—La—Co-based, sintered ferrite magnets containing more Ca than Sr when the Co content is 0.18 or less by atomic ratio.
JP 2018-30751 A discloses a Ca—La—Co ferrite compound having a hexagonal M-type magnetoplumbite structure and a composition by atomic ratio of metal elements of Ca, La, Fe and Co, which is represented by the general formula of Ca1−xLaxFe2n−zCoz, wherein x, z and n meet 0.3≤x≤0.6, 0.1≤z≤0.24, and 4.5≤n≤5.5. In this Ca—La—Co ferrite compound, the Co content is 0.1-0.24 by atomic ratio.
However, because the Ca—La—Co ferrite compound of JP 2018-30751 A does not contain Sr and/or Ba, the La content x is as high as 0.3≤x≤0.6. In Examples of JP 2018-30751 A, Samples 1-4 have as high La contents x as 0.450-0.550, though the Co contents z are as low as 0.090-0.180. Particularly Samples 1 and 2 of Comparative Examples having as low Co contents z as 0.090 and 0.095 have as high La content x as 0.550, with low saturation magnetization σs and anisotropic magnetic field HA. Also, even in Samples 3 and 4 having Co contents z of 0.134 and 0.180, the La contents x are as high as 0.524 and 0.450. To lower the material cost of sintered ferrite magnets, it is important to reduce not only the Co content but also the content of expensive La. Accordingly, the Ca—La—Co ferrite compound of JP 2018-30751 A is not sufficiently satisfactory from the aspect of cost reduction despite high performance.
Object of the Invention
Accordingly, an object of the present invention is to provide a sintered ferrite magnet having magnetic properties on the same level as or higher than those of conventional SrLaCo magnets and CaLaCo magnets, even with reduced Co content, and its production method, and calcined ferrite for providing such a sintered ferrite magnet.
SUMMARY OF THE INVENTION
Thus, the calcined ferrite of the present invention has a composition of metal elements of Ca, R, A, Fe and Co, which is represented by the general formula of Ca1−x−yRxAyFe2n−zCoz, wherein R is at least one of rare earth elements indispensably including La; A is Sr and/or Ba; x, y, z and n represent the atomic ratios of Ca, R, A, Fe and Co; 2n represents a molar ratio expressed by 2n=(Fe+Co)/(Ca+R+A); and x, y, z and n meet the following conditions:

0.30≤(1−x−y)≤0.55,

0.25≤x≤0.35,

0.15≤y≤0.40,

(1−x−y)>y, 

0<z≤0.18, and

9.0≤(2n−z)<11.0.

In the calcined ferrite of the present invention, the atomic ratio (1−x−y) preferably meets 0.40≤(1−x−y)≤0.50.
In the calcined ferrite of the present invention, the atomic ratio y preferably meets 0.20≤y≤0.35.
In the calcined ferrite of the present invention, the atomic ratio z preferably meets 0<z≤0.17.
In the calcined ferrite of the present invention, the atomic ratio (2n−z) preferably meets 9.0≤(2n−z)≤10.5.
In the calcined ferrite of the present invention, the atomic ratio (2n−z) preferably meets 9.0≤(2n−z)≤10.0.
The sintered ferrite magnet of the present invention has a composition of metal elements of Ca, R, A, Fe and Co, which is represented by the general formula of Ca1−x−yRxAyFe2n−zCoz, wherein R is at least one of rare earth elements indispensably including La; A is Sr and/or Ba; x, y, z and n represent the atomic ratios of Ca, R, A, Fe and Co; 2n represents a molar ratio expressed by 2n=(Fe+Co)/(Ca+R+A); and x, y, z and n meet the following conditions:

0.15≤x≤0.35,

0.05≤y≤0.40,

(1−x−y)>y, 

0<z≤0.18, and

7.5≤(2n−z)<11.0.

In the sintered ferrite magnet of the present invention, the atomic ratio (1−x−y) preferably meets 0.40≤(1−x−y)≤0.50.
In the sintered ferrite magnet of the present invention, the atomic ratio y preferably meets 0.20≤y≤0.35.
In the sintered ferrite magnet of the present invention, the atomic ratio z preferably meets 0<z≤0.17.
In the sintered ferrite magnet of the present invention, the atomic ratio (2n− z) preferably meets 7.5≤(2n− z)≤10.5.
In the sintered ferrite magnet of the present invention, the atomic ratio (2n− z) preferably meets 7.5≤(2n− z)≤10.0.
The sintered ferrite magnet of the present invention may further contain more than 0% and 1.5% or less by mass of Si as SiO2.
The method of the present invention for producing the above sintered ferrite magnet comprises the steps of mixing raw material powders containing metal elements of Ca, R, A, Fe and Co to prepare a raw material powder mixture having a metal element composition represented by the general formula of Ca1−x−yRxAyFe2n−zCoz, wherein R is at least one of rare earth elements indispensably including La; A is Sr and/or Ba; x, y, z and n represent the atomic ratios of Ca, R, A, Fe and Co; 2n represents a molar ratio expressed by 2n=(Fe+Co)/(Ca+R+A); and x, y, z and n meet the following conditions:

0.30≤(1−x−y)≤0.55,

0.25≤x≤0.35,

0.15≤y≤0.40,

(1−x−y)>y, 

0<z≤0.18, and

9.0≤(2n−z)<11.0,

calcining the resultant raw material powder mixture,
pulverizing the resultant calcined body,
molding the resultant calcined body powder, and
sintering the resultant green body.
In the production method of the present invention, after the calcining step and before the molding step, (a) more than 0% and 1.5% or less by mass of SiO2, or (b) more than 0% and 1.5% or less by mass of SiO2 and more than 0% and 1.5% or less by mass of CaCO3 as CaO may be added to 100% by mass of the calcined body or calcined body powder.
Effects of the Invention
The present invention can provide a sintered ferrite magnet having high Br and HcJ with a lower Co content than those of conventional SrLaCo magnets and CaLaCo magnets, by adjusting the composition of metal elements of Ca, R, A, Fe and Co. By having the composition of the present invention, magnetic properties higher than those of conventional SrLaCo magnets and comparable to those of conventional CaLaCo magnets can be obtained even with the Co content of 0.18 or less by atomic ratio, and further magnetic properties comparable to those of conventional SrLaCo magnets can be obtained even when the Co content is reduced to less than 0.15 by atomic ratio. Because the sintered ferrite magnet of the present invention, whose Co content is reduced while keeping magnetic properties on the same level as or higher than those of conventional SrLaCo magnets and/or CaLaCo magnets, has high performance with low cost, it can be suitably used for various motors, etc.


DESCRIPTION OF THE PREFERRED EMBODIMENTS
[1] Calcined Ferrite
The calcined ferrite of the present invention has a composition of metal elements of Ca, R, A, Fe and Co, which is represented by the general formula of Ca1−x−yRxAyFe2n−zCoz, wherein R is at least one of rare earth elements indispensably including La; A is Sr and/or Ba; x, y, z and n represent the atomic ratios of Ca, R, A, Fe and Co; 2n represents a molar ratio expressed by 2n=(Fe+Co)/(Ca+R+A); and x, y, z and n meet the following conditions:

0.30≤(1−x−y)≤0.55,

0.25≤x≤0.35,

0.15≤y≤0.40,

(1−x−y)>y, 

0<z≤0.18, and

9.0≤2n−z<11.0.

In the calcined ferrite of the present invention, R is at least one of rare earth elements indispensably including La. When other rare earth elements than La are contained, their amounts are preferably 50% or less by mol of the total amount of R. The atomic ratio x (R content) meets the condition of 0.25≤x≤0.35. When the atomic ratio x is less than 0.25 or more than 0.35, high Br and HcJ cannot be obtained. The lower limit of the atomic ratio x is preferably 0.275, and the upper limit of the atomic ratio x is preferably 0.325. Accordingly, the preferred range of the atomic ratio x is 0.275-0.325.
A is Sr and/or Ba. The atomic ratio y (A content) meets the condition of 0.15≤y≤0.40. When the atomic ratio y is less than 0.15 or more than 0.40, high Br and HcJ cannot be obtained. The range of the atomic ratio y is preferably 0.20≤y≤0.35, more preferably 0.20≤y≤0.30.
The atomic ratio (1− x−y) (Ca content) meets the condition of 0.30≤(1− x−y)≤0.55. When the atomic ratio (1− x−y) is less than 0.30 or more than 0.55, high Br and HcJ cannot be obtained. The preferred range of the atomic ratio (1−x−y) is 0.40≤(1−x−y)≤0.50.
The atomic ratio (1− x−y) (Ca content) and the atomic ratio y (A content) meet the relation of (1− x−y)>y. When this relation is not met, high Br and HcJ cannot be obtained.
The atomic ratio z (Co content) meets the condition of 0<z≤0.18. When the atomic ratio z is more than 0.18, the amount of Co used cannot be reduced sufficiently. On the other hand, the atomic ratio z of 0 (no Co contained) leads to low HcJ. The upper limit of the atomic ratio z is preferably 0.17. Also, the lower limit of the atomic ratio z is preferably 0.08, more preferably 0.1. Accordingly, the preferred range of the atomic ratio z is 0≤z≤0.17, and preferred examples of the atomic ratio z within this range are 0.08≤z≤0.18, and 0.08≤z≤0.17, 0.1≤z≤0.18, 0.1≤z≤0.17, etc.
The atomic ratio (2n− z) (Fe content) meets the condition of 9.0≤(2n− z)<11.0. When the atomic ratio (2n− z) is less than 9.0 or 11.0 or more, high Br and HcJ cannot be obtained. The range of the atomic ratio (2n− z) is preferably 9.0≤(2n− z)≤10.5, further preferably 9.0≤(2n− z)≤10.0.
While the composition of metal elements of Ca, R, A, Fe and Co is represented by the above general formula (atomic ratio), the composition including oxygen (O) is represented by the general formula of Ca1−x−yRxAyFe2n−zCozOα. The molar ratio α of oxygen is basically 19, though variable depending on the valences of Fe and Co, and the values of x, y and z and n. Also, the ratio of oxygen to metal elements changes depending on the vacancy of oxygen when sintered in a reducing atmosphere, the change of the valences of Fe and Co in a ferrite phase, etc. Accordingly, the molar ratio α of oxygen in actual calcined ferrite may be deviated from 19. Therefore, the present invention uses the composition of metal elements by atomic ratio, which can most easily identify the composition of the calcined or sintered ferrite.
A main phase constituting the calcined ferrite of the present invention is a compound phase (ferrite phase) having a hexagonal magnetoplumbite (M-type) structure. In general, magnetic materials, particularly sintered magnets, are composed of pluralities of compounds, and a compound determining their properties (physical properties, magnetic properties, etc.) is defined as a “main phase.”
The term of “having a hexagonal magnetoplumbite (M-type) structure” means that an X-ray diffraction pattern of a hexagonal magnetoplumbite (M-type) structure is mainly observed when the X-ray diffraction of calcined ferrite is measured under general conditions.
[2] Production Method of Sintered Ferrite Magnet
The method of the present invention for producing a sintered ferrite magnet through the above calcined ferrite will be explained in detail below.
The method of the present invention for producing a sintered ferrite magnet comprises the steps of mixing raw material powders containing metal elements of Ca, R, A, Fe and Co to prepare a raw material powder mixture having a metal element composition represented by the above general formula of Ca1−x−yRxAyFe2n−zCoz, in which x, y, z and n meet the following conditions:

0.30≤(1−x−y)≤0.55,

0.25≤x≤0.35,

0.15≤y≤0.40,

(1−x−y)>y, 

0<z≤0.18, and

9.0≤(2n−z)<11.0,

calcining the resultant raw material powder mixture,
pulverizing the resultant calcined body,
molding the resultant calcined body powder, and
sintering the resultant green body.
(1) Mixing Step of Raw Material Powders
Usable as raw material powders are compounds such as oxides, carbonates, hydroxides, nitrates, chlorides, etc. of these metals regardless of their valences. Ca compounds include carbonate, oxide, chloride, etc. of Ca. La compounds include oxides such as La2O3, etc., hydroxides such as La(OH)3, etc., carbonates such as La2(CO3)3.8H2O, etc. The compounds of the element A include carbonates, oxides, chlorides, etc. of Sr and/or Ba. Fe compounds include iron oxides, iron hydroxides, iron chlorides, mill scale, etc. Co compounds include oxides such as CoO, Co3O4, etc., hydroxides such as COOH, Co(OH)2, etc., carbonates such as CoCO3, etc., and basic carbonates such as m2CoCO3.m3Co(OH)2.m4H2O (m2, m3 and m4 are positive numbers), etc.
To accelerate a calcining reaction, up to about 1% by mass of B (boron)-containing compounds such as B2O3, H3BO3, etc. may be added to 100% by mass in total of raw material powders, if necessary. Particularly the addition of H3BO3 is effective for improving magnetic properties. The amount of H3BO3 added is preferably 0.3% or less by mass, and more preferably about 0.1% by mass. Because H3BO3 effectively controls the shape and size of crystal grains in sintering, it is added preferably after calcining (before fine pulverization or sintering), or may be added both before and after calcining.
Raw material powders meeting the above composition of the calcined ferrite of the present invention are mixed to obtain a raw material powder mixture. The mixing of the raw material powders may be conducted either in a wet or dry condition. By stirring with media such as steel balls, etc., the raw material powders can be mixed more uniformly. In the case of wet mixing, water is preferably used as a dispersion medium. To increase the dispersibility of the raw material powders, known dispersants such as ammonium polycarboxylates, calcium gluconate, etc. may be used. A raw material mixture slurry may be calcined before or after dewatering.
(2) Calcining Step
The raw material powder mixture obtained by dry or wet mixing is heated by an electric furnace, a gas furnace, etc. to form a ferrite compound having a hexagonal magnetoplumbite (M-type) structure by a solid phase reaction. This process is called “calcining,” and the resultant compound is called “calcined body.” Accordingly, the calcined ferrite of the present invention may be called “ferrite compound.”
In the calcining step, a solid phase reaction forming a ferrite phase proceeds as the temperature rises. When the calcining temperature is lower than 1100° C., unreacted hematite (Fe2O3) remains, resulting in low magnetic properties. On the other hand, when the calcining temperature exceeds 1450° C., crystal grains grow too much, needing much time for a pulverization step. Accordingly, the calcining temperature is preferably 1100-1450° C. The calcining time is preferably 0.5-5 hours.
(3) Pulverizing Step of Calcined Body
The calcined body obtained through the above step is coarsely pulverized by a hammer mill, etc., and then finely pulverized by a vibration mill, a jet mill, a ball mill, an attritor, etc., to obtain a calcined body powder (finely pulverized powder). The calcined body powder preferably has an average particle size of about 0.4-1.2 μm, and more preferably about 0.4-0.8 μm. The average particle size of the calcined body powder is further preferably 0.5-0.65 μm when improvement in magnetic properties is important. The average particle size of powder is measured by an air permeability method using a specific surface area meter of powder (for example, SS-100 available from Shimadzu Corporation), etc. The pulverization step of the calcined body may be conducted by dry or wet pulverization or both. In the case of wet pulverization, water and/or a non-aqueous solvent (an organic solvent such as acetone, ethanol, xylene, etc.) are used as a dispersion medium. Typically, a slurry comprising the calcined body and water (dispersion medium) is formed. A known dispersant and/or surfactant in an amount of 0.2-2% by mass on a solid basis may be added to the slurry. After the wet pulverization, the slurry may be concentrated.
(4) Molding Step of Calcined Body Powder
In the molding step, the slurry after the pulverization step is press-molded in or without a magnetic field while removing the dispersion medium. By press molding in a magnetic field, the crystal orientation of powder particles can be aligned (oriented), to drastically increase magnetic properties. To improve the orientation, 0.1-1% by mass each of a dispersant and a lubricant may be added to 100% by mass of the slurry before molding. Before molding, the slurry may be concentrated if necessary. The concentration is preferably conducted by centrifugal separation, filter-pressing, etc.
After the calcining step and before the molding step, a sintering additive may be added to the calcined body or calcined body powder (coarsely or finely pulverized powder). The sintering additives are preferably SiO2 alone, or both SiO2 and CaCO3. The sintered ferrite magnet of the present invention is categorized in a CaLaCo magnet as is clear from its composition. Because the CaLaCo magnet contains Ca as a main phase component, a liquid phase enabling sintering is formed without adding sintering additives such as SiO2, CaCO3, etc., unlike in SrLaCo magnets. Namely, without adding SiO2 and CaCO3 mainly forming grain boundary phases in sintered ferrite magnets, the sintered ferrite magnet of the present invention can be produced. However, to suppress decrease in HJ, SiO2 and CaCO3 in amounts described below may be added as sintering additives.
The amount of SiO2 if added is preferably more than 0% and 1.5% or less by mass per 100% by mass of the calcined body or calcined body powder. Also, the amount of CaCO3 if added is preferably more than 0% and 1.5% or less by mass as CaO per 100% by mass of the calcined body or calcined body powder. The addition of sintering additives may be either before, during or after the pulverizing step, as long as it is before molding. In addition to SiO2 and CaCO3, Cr2O3, Al2O3, etc. may be added as sintering additives. Their amounts may be 1% or less by mass each.
The amount of CaCO3 added is converted to the amount of CaO. The amount (% by mass) of CaCO3 added is calculated from the amount of CaO (% by mass) by the formula of (molecular weight of CaCO3×amount of CaO)/molecular weight of CaO. For example, when 0.5% by mass of CaCO3 as CaO is to be added, the amount of CaCO3 added is (100.09×0.5% by mass)/56.08=0.892% by mass, because the molecular weight of CaCO3 is 100.09=40.08 (atomic weight of Ca)+12.01 (atomic weight of C)+48.00 (atomic weight of 0×3), and the molecular weight of CaO is 56.08=40.08 (atomic weight of Ca)+16.00 (atomic weight of 0).
(5) Sintering Step of Green Body
A green body obtained by press molding is degreased if necessary, and then sintered. The sintering is conducted in an electric furnace, a gas furnace, etc. The sintering is conducted in an atmosphere having an oxygen concentration of preferably 10% or more by volume. The oxygen concentration in the sintering atmosphere is more preferably 20% or more by volume, and most preferably 100% by volume. The sintering temperature is preferably 1150-1250° C. The time of keeping the sintering temperature (sintering time) is preferably 0 hour (no holding time at sintering temperature) to 2 hours.
As shown in Examples below, the present invention uses, for example, (a) a sintering condition comprising increasing the temperature at an average rate of 400° C./hour in a temperature range from room temperature to the sintering temperature, keeping the sintering temperature for a predetermined period of time (sintering time) (including no holding time), and then lowering the temperature at an average rate of 300° C./hour in a temperature range from the sintering temperature to 800° C., (b) a sintering condition comprising increasing the temperature at an average rate of 600° C./hour or more and 1000° C./hour or less in a temperature range from 800° C. to the sintering temperature, keeping the sintering temperature for the sintering time (including no holding time), and then lowering the temperature at an average rate of 1000° C./hour or more in a temperature range from the sintering temperature to 800° C., etc.
The latter sintering condition (b) can shorten a lead time because of very high temperature-increasing and temperature-lowering rates. Though the temperature-increasing rate in a temperature range of up to 800° C. is not particularly restricted, it is preferably the same as the temperature-increasing rate in a temperature range from 800° C. to the sintering temperature, taking into account the shortening of a lead time. Namely, the average temperature-increasing rate is preferably 600° C./hour or more and 1000° C./hour or less in an entire temperature range from room temperature or a temperature in the furnace (preheating temperature, etc.) to the sintering temperature. Further, though the temperature-lowering rate in a temperature range from 800° C. to near room temperature is not particularly restricted, it is preferably the same as or close to the temperature-lowering rate in a temperature range from the sintering temperature to 800° C., taking into account the shortening of a lead time. Incidentally, the temperature used in the embodiments of the present invention represents the temperature of an object to be heat-treated (green body or sintered body). The measurement of the temperature is conducted by an R-type thermocouple in contact with the object to be heat-treated in a sintering furnace.
After the sintering step, a final sintered ferrite magnet is produced through known production steps such as a machining step, a cleaning step, an inspection step, etc.
[3] Sintered Ferrite Magnet
The sintered ferrite magnet of the present invention obtained through the above steps has a composition of metal elements of Ca, R, A, Fe and Co, which is represented by the general formula of Ca1−x−yRxAyFe2n−zCOz, wherein R is at least one of rare earth elements indispensably including La; A is Sr and/or Ba; x, y, z and n represent the atomic ratios of Ca, R, A, Fe and Co; 2n represents a molar ratio expressed by 2n=(Fe+Co)/(Ca+R+A); and x, y, z and n meet the following conditions:

0.15≤x≤0.35,

0.05≤y≤0.40,

(1−x−y)>y, 

0<z≤0.18, and

7.5≤(2n−z)<11.0.

Because a liquid phase is generated in the calcined ferrite of the present invention without adding SiO2 and CaCO3 as sintering additives, enabling the sintering of the calcined ferrite as described above, the composition of the sintered ferrite magnet is basically the same as that of the calcined ferrite when CaCO3 is not added, as long as impurities which may be contained during the production steps are not taken into account.
On the other hand, when CaCO3 is added as a sintering additive, the sintered ferrite magnet has a higher percentage of Ca than in the calcined body, with lower percentages of other elements. For example, when 1.5% by mass of CaCO3 as CaO is added as a sintering additive to the calcined ferrite of the present invention, the amounts of R, A and Fe are changed at maximum from 0.25≤x≤0.35, 0.15≤y≤0.40, and 9.0≤(2n− z)<11.0 in the calcined body, to 0.15≤x≤0.35, 0.05≤y≤0.40, and 7.5≤(2n− z)<11.0 in the sintered magnet.
The preferred ranges of the atomic ratios (1− x−y), y and z in the sintered ferrite magnet are 0.40≤(1− x−y)≤0.50, 0.20≤y≤0.35, and 0<z≤0.17. Also, the range of the atomic ratio (2n− z) in the sintered ferrite magnet is preferably 7.5≤(2n− z)≤10.5, and further preferably 7.5≤(2n− z)≤10.0. The lower limit, upper limit and range of the Co content z in the sintered ferrite magnet may be the same as in the calcined ferrite.
The composition including oxygen (O) and the definitions of a main phase and a hexagonal magnetoplumbite (M-type) structure in the sintered ferrite magnet of the present invention are the same as those of the calcined ferrite of the present invention. Though the ranges of the atomic ratios x, y and (2n− z) in the sintered ferrite magnet differ from those in the calcined ferrite, reasons for limiting the atomic ratios x, y, z and (2n− z) in the sintered ferrite magnet are the same as in the calcined ferrite. Accordingly, their explanations are omitted. Incidentally, the range of the atomic ratio (1− x−y) also inevitably changes by the changes of the ranges of the atomic ratios x and y.
When more than 0% and 1.5% or less by mass of SiO2 is added as a sintering additive to 100% by mass of the calcined body or the calcined body powder, SiO2 forms a liquid phase during sintering, constituting one component in grain boundary phases in the sintered ferrite magnet, the resultant sintered ferrite magnet contains more than 0% and 1.5% or less by mass of Si as SiO2. Though the inclusion of Si results in relative decrease in the amounts of metal elements of Ca, R, A, Fe and Co in the sintered ferrite magnet, the percentage of each metal element does not change in the general formula of Ca1−x−yRxAyFe2n−zCoz. Incidentally, the Si content as SiO2 is determined by converting the percentages (% by mass) of Ca, Sr, Ba, La, Fe, Co and Si measured by the component analysis (for example, ICP atomic emission spectroscopy) of the sintered ferrite magnet to the percentages (% by mass) of CaCO3, SrCO3, BaCO3, La(OH)3, Fe2O3, Co3O4 and SiO2. In the case of containing other rare earth elements R′ than La, the Si content as SiO2 is similarly determined by converting the percentages (% by mass) of Ca, Sr, Ba, La, R′, Fe, Co and Si to the percentages (% by mass) of CaCO3, SrCO3, BaCO3, La(OH)3, R′ oxide, Fe2O3, Co3O4 and SiO2.
The present invention will be explained in further detail by Examples below, without intention of restricting the present invention thereto.
Example 1
CaCO3 powder, La(OH)3 powder, SrCO3 powder, Fe2O3 powder and Co3O4 powder were formulated at percentages giving the atomic ratios (1− x−y), x, y, z and (2n− z) shown in Table 1, in the general formula of Ca1−x−yLaxSryFe2n−zCoz showing a composition of metal elements of Ca, R, A, Fe and Co, and mixed for 4 hours in a wet ball mill with 0.1% by mass of H3BO3 powder added to 100% by mass in total of them. Each of the resultant mixtures was dried and granulated to obtain 30 types of raw material powder mixtures (Samples 1-30).
All of 30 types of the raw material powder mixtures were calcined at the calcining temperatures shown in Table 1 for 3 hours in the air, to obtain 30 types of calcined bodies.
Each calcined body was coarsely pulverized by a small mill to obtain each coarse calcined body powder. With CaCO3 powder (amount expressed as CaO) and SiO2 powder in the amounts shown in Table 1 added to 100% by mass of each coarse calcined body powder, each coarse calcined body powder was finely pulverized in a wet ball mill containing water as a dispersion medium to an average particle size [measured by an air permeability method using a specific surface area meter of powder (SS-100 available from Shimadzu Corporation)] shown in Table 1, to obtain 30 types of finely pulverized slurries.
Each finely pulverized slurry was press-molded under pressure of about 2.4 MPa in a magnetic field of about 1 T, in a parallel-magnetic-field molding machine (vertical-magnetic-field molding machine), in which the direction of pressing was in parallel with the direction of a magnetic field, while removing water, to obtain 30 types of green bodies.
Each green body was placed in a sintering furnace, and sintered under the sintering condition A or B shown in Table 1. In the sintering condition A, the temperature was increased at an average rate of 1000° C./hour in a temperature range from room temperature to the sintering temperature shown in Table 1, while flowing air at a flow rate of 10 L/minute in the sintering furnace, and sintering was conducted at that sintering temperature for 1 hour. After sintering, a heater in the sintering furnace was shut off, and the flow rate of air was changed from 10 L/minute to 40 L/minute, to lower the temperature at an average rate of 1140° C./hour in a temperature range from the sintering temperature to 800° C. The resultant sintered body was then left to cool to room temperature in the furnace. In the sintering condition B, the temperature was increased at an average rate of 400° C./hour in a temperature range from room temperature to the sintering temperature shown in Table 1, while flowing air at a flow rate of 10 L/minute in the sintering furnace, and sintering was conducted at that sintering temperature for 1 hour. After sintering, a heater in the sintering furnace was shut off to lower the temperature at an average rate of 300° C./hour in a temperature range from the sintering temperature to 800° C., with the flow rate of air kept at 10 L/minute. The resultant sintered body was then left to cool to room temperature in the furnace.
With respect to 30 types of the sintered ferrite magnets, the measurement results of Br, HcJ and Hk/HcJ are shown in Table 1. In Table 1, Samples 4 and 7 with * do not meet the composition conditions of the present invention, because the atomic ratios x of the rare earth element in their calcined bodies were less than 0.25. Other Samples (without *) than Samples 4 and 7 meet the composition conditions of the present invention. Incidentally, in a J-H curve, wherein J represents magnetization, and H represents the intensity of a magnetic field, Hk is a value of H at a position at which J is 0.95×Jr (Jr is residual magnetization=Br) in the second quadrant.
Table 1 shows atomic ratios when the raw material powders were formulated (formulation compositions). The atomic ratios in the sintered ferrite magnet (composition of the sintered magnet) can be calculated from the formulation composition, taking into account the amounts of H3BO3, etc. added before the calcining step and sintering additives (CaCO3 and SiO2) added after the calcining step and before the molding step, and the calculated values are basically the same as the values obtained by analyzing the sintered ferrite magnet by an ICP atomic emission spectroscope (for example, ICPV-1017 available from Shimadzu Corporation, etc.). The same is true in the atomic ratios in Table 2.








TABLE 1








Atomic Ratio












Sample
Ca
La
Sr
Co
Fe


No.
1 − x − y
x
y
z
2n − z





 1
0.50
0.30
0.20
0.13
9.50


 2
0.50
0.30
0.20
0.13
9.50


 3
0.50
0.25
0.25
0.13
9.50


  4*
0.50
0.20
0.30
0.13
9.50


 5
0.45
0.30
0.25
0.13
9.50


 6
0.45
0.25
0.30
0.13
9.50


  7*
0.45
0.20
0.35
0.13
9.50


 8
0.45
0.30
0.25
0.10
9.50


 9
0.45
0.30
0.25
0.10
9.50


10
0.45
0.30
0.25
0.11
9.50


11
0.45
0.30
0.25
0.11
9.50


12
0.45
0.30
0.25
0.12
9.50


13
0.45
0.30
0.25
0.12
9.50


14
0.45
0.30
0.25
0.15
9.50


15
0.45
0.30
0.25
0.15
9.50


16
0.45
0.30
0.25
0.18
9.50


17
0.45
0.30
0.25
0.18
9.50


18
0.40
0.30
0.30
0.13
9.50


19
0.45
0.275
0.275
0.15
9.50


20
0.45
0.275
0.275
0.15
9.50


21
0.45
0.325
0.225
0.15
9.50


22
0.45
0.325
0.225
0.15
9.50


23
0.425
0.325
0.25
0.15
9.50


24
0.425
0.325
0.25
0.15
9.50


25
0.45
0.30
0.25
0.17
9.50


26
0.45
0.30
0.25
0.17
9.50


27
0.45
0.325
0.225
0.17
9.50


28
0.45
0.325
0.225
0.17
9.50


29
0.45
0.35
0.20
0.17
9.50


30
0.45
0.35
0.20
0.17
9.50


















Average





Calcining
Amount 
Particle 

Sintering


Sample
Temp.
(% by mass)
Size(1)
Sintering
Temp.













No.
(° C.)
CaCO3
SiO2
(μm)
Condition
(° C.)





 1
1200
0.700
0.825
0.60
A
1200


 2
1200
0.700
0.775
0.60
A
1210


 3
1200
0.700
0.800
0.60
A
1200


  4*
1200
0.700
0.800
0.60
A
1200


 5
1200
0.700
0.800
0.60
A
1200


 6
1200
0.700
0.825
0.60
A
1200


  7*
1200
0.700
0.800
0.60
A
1200


 8
1200
0.700
0.925
0.60
A
1200


 9
1200
0.700
0.925
0.60
B
1200


10
1200
0.700
0.900
0.60
A
1200


11
1200
0.700
0.875
0.60
B
1200


12
1200
0.700
0.825
0.60
A
1200


13
1200
0.700
0.875
0.60
B
1200


14
1200
0.700
0.850
0.60
A
1200


15
1200
0.700
0.900
0.60
B
1200


16
1200
0.700
0.850
0.60
A
1200


17
1200
0.700
0.850
0.60
B
1200


18
1200
0.700
0.950
0.60
A
1200


19
1200
0.700
0.800
0.60
A
1200


20
1200
0.700
0.800
0.60
B
1200


21
1200
0.700
0.800
0.60
A
1200


22
1200
0.700
0.800
0.60
B
1200


23
1200
0.700
0.800
0.60
A
1200


24
1200
0.700
0.900
0.60
B
1200


25
1200
0.700
0.800
0.60
A
1200


26
1200
0.700
0.750
0.60
B
1200


27
1200
0.700
0.800
0.60
A
1200


28
1200
0.700
0.800
0.60
B
1200


29
1200
0.700
0.750
0.60
A
1200


30
1200
0.700
0.800
0.60
B
1200










Note: 


(1)Average particle size of pulverized powder in the finely 


pulverized slurry.













Sample
Br
HcJ
Hk/HcJ


No.
(T)
(kA/m)
(%)





 1
0.439
355
90.4


 2
0.441
348
89.0


 3
0.435
304
89.1


  4*
0.432
270
88.3


 5
0.436
375
88.3


 6
0.436
355
86.2


  7*
0.429
312
82.1


 8
0.435
347
93.1


 9
0.437
342
88.2


10
0.437
353
93.1


11
0.437
323
91.6


12
0.436
362
90.5


13
0.439
347
89.9


14
0.437
390
83.7


15
0.440
377
84.4


16
0.437
393
73.4


17
0.442
374
78.3


18
0.433
391
89.2


19
0.435
380
84.0


20
0.438
352
89.8


21
0.437
394
85.0


22
0.440
366
91.5


23
0.437
387
86.8


24
0.439
389
91.5


25
0.439
397
78.3


26
0.440
370
86.2


27
0.440
405
82.7


28
0.440
377
88.5


29
0.442
407
87.6


30
0.440
395
90.3









As shown in Table 1, Samples 1-3, 5, 6, 8-13 and 18 having atomic ratios z (Co contents) of less than 0.15 with the atomic ratios of other metal elements adjusted to meet the composition conditions of the present invention had Br of 0.433-0.441 T and HcJ of 304-391 kA/m. This indicates that sintered ferrite magnets meeting the composition conditions of the present invention had magnetic properties on the same level as those of conventional SrLaCo magnets, even with smaller Co contents than in conventional SrLaCo magnets.
Also, Samples 14-17 and 19-30 having atomic ratios z (Co contents) of 0.15-0.18 with the atomic ratios of other metal elements adjusted to meet the composition conditions of the present invention had Br of 0.435-0.442 T and HcJ of 352-407 kA/m, exhibiting magnetic properties exceeding those of conventional SrLaCo magnets, with Co contents on the same level as in conventional SrLaCo magnets. Particularly, the sintered ferrite magnets having atomic ratios x (La contents) in a range of 0.325≤x≤0.35 and atomic ratios z (Co contents) in a range of 0.17≤z≤0.18 had magnetic properties comparable to those of conventional CaLaCo magnets (La content: about 0.5 by atomic ratio, and Co content: about 0.3 by atomic ratio), with reduced La and Co contents than in the conventional CaLaCo magnets.
On the other hand, Samples 4 and 7 having atomic ratios x (La contents) of 0.20 exhibited Br of 0.432 T or less and HcJ of 312 kA/m or less, lower magnetic properties than in conventional SrLaCo magnets, because they did not meet the condition of 0.25≤x≤0.35 in the present invention.
As is clear from Table 1, pairs of Samples (8 and 9, 10 and 11, 12 and 13, 14 and 15, 16 and 17, 19 and 20, 21 and 22, 23 and 24, 25 and 26, 27 and 28, and 29 and 30) each having the same composition (the amount of SiO2 may differ slightly), which were produced under different sintering conditions A and B, had high Br and HcJ regardless of their sintering conditions. Particularly, sintering under the condition A tended to provide higher HcJ, and sintering under the condition B tended to provide higher Br.
Samples 16 and 17 having atomic ratios z (Co contents) of 0.18 and meeting the composition conditions of the present invention exhibited high Br and HcJ, despite slightly low Hk/HcJ. On the other hand, Samples 25-30 having atomic ratios z (Co contents) of 0.17 exhibited high Br and HcJ as well as high Hk/HcJ. These results indicate that the atomic ratio z (Co content) in a range of 0<z≤0.17 is preferable for applications needing high Hk/HcJ.
Example 2
7 types of sintered ferrite magnets (Samples 31-37) were produced in the same manner as in Example 1, except for changing the atomic ratio z (Co content) (Samples 31 and 32) and the atomic ratio (2n− z) (Fe content) (Samples 34-37), or using Ba as the element A (Sample 33), in the general formula of Ca1−x−yLaxAyFe2n−zCoz. All Samples 31-37 meet the composition conditions of the present invention. With respect to each sample, the formulation composition, the calcining temperature, the amounts of CaCO3 (as CaO) and SiO2 added, the average particle size after ball milling, the sintering condition, and the sintering temperature, as well as the Br, HcJ and Hk/HcJ of the sintered ferrite magnet are shown in Table 2.








TABLE 2








Atomic Ratio













Sample
Ca
La
Sr
Ba
Co
Fe


No.
1 − x − y
x
y
y
z
2n − z





31
0.45
0.30
0.25
0
0.09
9.50


32
0.45
0.30
0.25
0
0.08
9.50


33
0.45
0.30
0  
0.25
0.15
9.50


34
0.45
0.30
0.25
0
0.10
9.00


35
0.45
0.30
0.25
0
0.11
9.00


36
0.45
0.30
0.25
0
0.15
9.00


37
0.45
0.30
0.25
0
0.15
10.00


















Average





Calcining
Amount 
Particle 

Sintering


Sample
Temp.
(% by mass)
Size(1)
Sintering
Temp.













No.
(° C.)
CaCO3
SiO2
(μm)
Condition
(° C.)





31
1200
0.700
0.900
0.60
A
1200


32
1200
0.700
0.900
0.60
A
1200


33
1200
0.700
0.900
0.60
A
1200


34
1200
0.700
1.050
0.60
A
1200


35
1200
0.700
1.050
0.60
A
1200


36
1200
0.700
1.000
0.60
A
1200


37
1200
0.700
0.700
0.60
A
1200










Note: 


(1)Average particle size of pulverized powder in the finely 


pulverized slurry.













Sample
Br
HcJ
Hk/HcJ


No.
(T)
(kA/m)
(%)





31
0.435
346
92.1


32
0.435
334
93.3


33
0.436
331
83.8


34
0.434
356
94.0


35
0.431
370
93.4


36
0.432
424
84.3


37
0.430
376
88.9









As is clear from Table 2, Samples 31 and 32 having lower atomic ratios z (Co contents z<0.10) than in Example 1 (z≥0.10) had Br of 0.435 T and HcJ of 334-346 kA/m. This indicates that as long as the composition conditions of the present invention are met, sintered ferrite magnets having magnetic properties on the same level as those of conventional SrLaCo magnets can be obtained even though the Co content is lower than in Example 1.
Sample 33 comprising Ba in place of Sr as the element A had Br on the same level as that of Sample 14 in Example 1, which had substantially the same composition except for comprising Sr as the element A, and slightly lower HcJ than that of Sample 14, but the HcJ of Sample 33 was on the same level as those of conventional SrLaCo magnets. This indicates that as long as the composition conditions of the present invention are met, sintered ferrite magnets having magnetic properties on the same level as or higher than those of conventional SrLaCo magnets can be obtained even though Ba is used in place of Sr.
It was found that Samples 34-36 having atomic ratios (2n− z) of the Fe content=9.00, which was lower than in Example 1 (9.50) within the composition range of the present invention, had higher HcJ than those of Samples in Example 1 having the same atomic ratios z (Co contents) as those of Samples 34-36, and that increase in the atomic ratio z (Co content) from 0.10 to 0.15 resulted in higher HcJ. Also, Sample 37 having a higher atomic ratio (2n− z) of the Fe content=10.00 than in Example 1 (9.50) within the composition range of the present invention had Br slightly lower than in Example 1 but on the same level as those of conventional SrLaCo magnets.

## Claims

1. A sintered ferrite magnet having a composition of metal elements of Ca, R, A, Fe and Co, which is represented by the general formula of Ca1-x-y′RxAy′Fe2n-zCoz, wherein R is at least one of rare earth elements indispensably including La; A is Sr; x, y′, z and n represent the atomic ratios of Ca, R, A, Fe and Co; 2n represents a molar ratio expressed by 2n=(Fe+Co)/(Ca+R+A); and x, y′, z and n meet the following conditions:


0.425≤(1−x−y′)≤0.55,



0.15≤x≤0.35,



0.05≤y′≤0.40,



(1−x−y′)>y′, 



0<z≤0.18, and



7.5≤(2n−z)<11.0,


wherein said sintered ferrite magnet further contains more than 0% and 1.0% or less by mass of Si as SiO2.

2. The sintered ferrite magnet according to claim 1, wherein said atomic ratio (1−x−y′) meets 0.425>(1−x−y′)≤0.50.

3. The sintered ferrite magnet according to claim 1, wherein said atomic ratio y′ meets 0.20≤y′≤0.40.

4. The sintered ferrite magnet according to claim 1, wherein said atomic ratio y′ meets 0.20≤y′≤0.35.

5. The sintered ferrite magnet according to claim 1, wherein said atomic ratio z meets 0≤z≤0.17.

6. The sintered ferrite magnet according to claim 1, wherein said atomic ratio z meets 0≤z≤0.15.

7. The sintered ferrite magnet according to claim 1, wherein said atomic ratio (2n−z) meets 7.5≤(2n−z)≤10.5.

8. The sintered ferrite magnet according to claim 1, wherein said atomic ratio (2n−z) meets 7.5≤(2n−z)≤10.0.

9. The sintered ferrite magnet according to claim 1, wherein said atomic ratios z and (2n−z) meet 0.0084≤z/(2n−z)≤0.0167.

10. A method for producing the sintered ferrite magnet recited in claim 1, comprising the steps of
mixing raw material powders containing metal elements of Ca, R, A, Fe and Co to prepare a raw material powder mixture having a metal element composition represented by the general formula of Ca1−x−y′RxAy′Fe2n-zCoz, wherein R is at least one of rare earth elements indispensably including La; A is Sr; x, y′, z and n represent the atomic ratios of Ca, R, A, Fe and Co; 2n represents a molar ratio expressed by 2n=(Fe+Co)/(Ca+R+A); and x, y′, z and n meet the following conditions:


0.425≤(1−x−y′)≤0.55,



0.15≤x≤0.35,



0.05≤y′≤0.40,



(1−x−y′)>y′, 



0<z≤0.18, and



9.0≤2n−z)<11.0,


calcining the resultant raw material powder mixture,
pulverizing the resultant calcined body,
molding the resultant calcined body powder, and
sintering the resultant green body,

wherein more than 0% and 1.0% or less by mass of SiO2 is added to 100% by mass of said calcined body or calcined body powder, after said calcining step and before said molding step.

11. The method for producing a sintered ferrite magnet according to claim 10, wherein more than 0% and 1.5% or less by mass of CaCO3 as CaO is further added to 100% by mass of said calcined body or calcined body powder, after said calcining step and before said molding step.

12. The method for producing a sintered ferrite magnet according to claim 10, wherein more than 0% and 0.7% or less by mass of CaCO3 as CaO is further added to 100% by mass of said calcined body or calcined body powder, after said calcining step and before said molding step.

13. The method for producing a sintered ferrite magnet according to claim 10, wherein said atomic ratio (1−x−y′) meets 0.425≤(1−x−y′)≤0.50.

14. The method for producing a sintered ferrite magnet according to claim 10, wherein said atomic ratio z meets 0<z≤0.15.

15. The method for producing a sintered ferrite magnet according to claim 10, wherein said atomic ratios z and (2n−z) meet 0.0084≤z/(2n−z)≤0.0167.