JP5804370B2 - Method for producing oxide magnetic material - Google Patents

Description

  The present invention relates to a method for producing an oxide magnetic material.

Ferrite sintered magnets are used in various applications such as various motors, generators, and speakers. As typical ferrite sintered magnets, Sr ferrite (SrFe ₁₂ O ₁₉ ) and Ba ferrite (BaFe ₁₂ O ₁₉ ) having a hexagonal M-type magnetoplumbite structure are known. These sintered ferrite magnets are manufactured at a relatively low cost by powder metallurgy using iron oxide and a carbonate such as strontium (Sr) or barium (Ba) as raw materials.

In recent years, there has been a demand for higher performance of sintered ferrite magnets for the purpose of reducing the size, weight, and efficiency of electrical parts for automobiles, parts for electrical equipment, and the like. In particular, motors used in automotive electrical components have a high residual magnetic flux density B _r (hereinafter simply referred to as “B _r ”) and a high magnetic resistance that is not demagnetized by a demagnetizing field generated when the thickness is reduced. There is a demand for a sintered ferrite magnet having a magnetic force H _cJ (hereinafter simply referred to as “H _cJ ”).

Order to improve the magnetic properties of the sintered ferrite magnet was replaced with the rare earth element La, etc. Some of the Sr in the above Sr ferrite, by substituting a part of Fe with Co, the H _cJ and B _r Improvements have been proposed in Patent Document 1 (Japanese Patent Laid-Open No. 10-149910), Patent Document 2 (Japanese Patent Laid-Open No. 11-154604), and the like.

  Sr ferrite described in Patent Documents 1 and 2 in which a part of Sr is substituted with a rare earth element such as La and a part of Fe is substituted with Co or the like (hereinafter referred to as “SrLaCo ferrite”) has excellent magnet characteristics, Since the contents of expensive La and Co are relatively low and can be provided at a low cost, they are being widely used in various applications in place of the conventional Sr ferrite and Ba ferrite, but further improvement in magnet characteristics is also desired.

In order to improve the magnetic properties of the SrLaCo ferrite, Patent Document 3 (WO 2004/027153), by substituting a part of Sr by Ca, improving _{H cJ} while maintaining a high _{B r} Propose that. However, a ferrite sintered magnet having a high _HcJ sufficient to satisfy market demand has not been obtained.

Patent Document 4 (Japanese Patent Application Laid-Open No. 2007-123511) includes a first pulverization step, a powder heat treatment step, and a second pulverization step, and the crystal particle size is 1.1 μm or less. by the ratio of the number is 95% or more, has proposed a method for improving the left H _cJ maintaining the B _r.

However, according to the method described in Patent Document 4, although _HcJ is improved, an increase in cost due to an increase in manufacturing steps is inevitable. In particular, SrLaCo ferrite containing an expensive element such as Co or La as an essential component has a slightly higher raw material cost than the conventional Sr ferrite, so that the process cost is further increased, which makes it economical. The most important feature of sintered ferrite magnets is that they are superior, and the price requirements in the market cannot be satisfied.

On the other hand, Ca ferrite is also known as a ferrite sintered magnet together with the Sr ferrite and Ba ferrite. Ca ferrite has a stable structure of CaO—Fe ₂ O ₃ or CaO-2Fe ₂ O ₃ and is known to form hexagonal ferrite by adding La. However, the obtained magnet characteristics are similar to those of the conventional Ba ferrite and are not sufficiently high.

Patent Document 5 (Japanese Patent Application Laid-Open No. 2000-223307) describes a _method of _replacing a part of Ca with a rare earth element such as La in order to improve the B _r and H _cJ of Ca ferrite and the temperature characteristics of H _cJ . a part of Fe discloses substituted Ca ferrite (hereinafter referred to as "CaLaCo ferrite") of Co or the like, the anisotropic magnetic field _{H a} of the CaLaCo ferrite is up to 10% or higher 20kOe or more as compared to the Sr ferrite It is described that the value of can be obtained.

However, CaLaCo ferrite according to Patent Document 5, the anisotropy field _H but having an _A at characteristic exceeding SrLaCo ferrite, _{B r} and _{H cJ} are comparable to SrLaCo ferrite, whereas squareness ratio _H k / H _cJ (hereinafter, simply referred to as “H _k / H _cJ ”) is very poor, cannot satisfy both high H _cJ and high H _k / H _cJ, and is applied to various uses such as motors It has not yet reached.

In order to improve the magnetic properties of the above CaLaCo ferrite, for example, Patent Document 6 (Japanese Patent Laid-Open No. 2006-104050) optimizes the molar ratio of each constituent element and the value of n, and contains La and Co at a specific ratio. CaLaCo ferrite is proposed, and Patent Document 7 (International Publication No. 2007/060757) proposes CaLaCo ferrite in which a part of Ca is replaced with La and Ba. 2007/077781) proposes a CaLaCo ferrite in which a part of Ca is replaced with La and Sr. However, even with the CaLaCo ferrite described in Patent Documents 5 to 7, a ferrite sintered magnet having a high _HcJ sufficient to satisfy market demands has not been obtained.

Furthermore, although the CaLaCo ferrite improved as described above has superior magnet characteristics compared to the SrLaCo ferrite, it contains higher amounts of expensive La and Co than the SrLaCo ferrite, so the raw material costs are high, and therefore it is commensurate with the price. _There is a strong demand for magnetic properties, particularly high _HcJ .

Patent Document 9 (Japanese Patent Laid-Open No. 2008-137879) and Patent Document 10 (International Publication No. 2008/105449) improve _HcJ by adopting the grinding process described in Patent Document 4 in the production process of CaLaCo ferrite. The technology which aimed at is disclosed. Although CaLaCo ferrites described in Patent Documents 9 and 10 have been improved in _HcJ , as in Patent Document 5, the cost is doubled with raw material costs and process costs, and there is a demand for price in the market. Can not be satisfied.

Thus, in SrLaCo ferrite and CaLaCo ferrite, the magnet characteristics are improved by improving the composition ratio as in Patent Document 3 and Patent Documents 6 to 8, or by improving the manufacturing method as in Patent Document 4 and Patent Documents 9 to 10. However, the improvement of the composition ratio does not provide a sintered ferrite magnet having _HcJ that is high enough to satisfy the market demand, and the improvement of the manufacturing method satisfies the price requirement in the market. There was a problem that I could not.

JP-A-10-149910 JP-A-11-154604 International Publication No. 2004/027153 JP 2007-123511 A JP 2000-223307 A JP 2006-104050 A International Publication No. 2007/060757 International Publication No. 2007/077781 JP 2008-137879 A International Publication No. 2008/105449

An object of the present invention, without causing soaring raw material costs and process costs, high _{B r} and _H k _{/ H cJ} can be improved while _{H cJ} was maintained, La and Co, such as SrLaCo ferrite or CaLaCo ferrite It is providing the manufacturing method of the oxide magnetic material containing this.

As a result of various studies in view of the above object, the inventors have focused on raw materials for producing oxide magnetic materials. Conventionally, as raw material powder of SrLaCo ferrite, SrCO ₃ , La ₂ O ₃ , Fe ₂ O ₃ , Co ₃ O _{4 and the} like, and as raw material powder of CaLaCo ferrite, CaCO ₃ , La ₂ O ₃ , SrCO ₃ , BaCO _{3 are used.} , Fe ₂ O ₃ , Co ₃ O _{4, and the} like, oxides, carbonates, hydroxides, chlorides, and the like of metal elements that are essential elements are used.

  The SrLaCo ferrite and CaLaCo ferrite described above are obtained by mixing the raw materials and then heating to form a ferrite compound having a hexagonal M-type magnetoplumbite structure by a solid phase reaction. This process is called “calcination” and the resulting compound is called “calcination”. If the ferrite compound is not sufficiently formed in the calcined body, the composition of the sintered magnet or the bonded magnet using the calcined body may be shifted in composition or a heterogeneous phase may be generated, leading to deterioration of the magnet characteristics.

  Therefore, in calcination, it is important to appropriately adjust the raw material particle size, mixing state, heating temperature, and the like so that the ferrite compound is sufficiently formed, and preferably a ferrite compound single phase. In other words, the formation state of the ferrite compound changes depending on what raw material is used, and consequently the magnet characteristics of the sintered magnet and the bonded magnet change.

The inventors have studied the applicability of conventionally used forms other than the oxides and carbonates of metal elements alone, which are essential elements, for example, compounds of essential elements, and a composite of La and Fe. Attention was focused on LaFeO ₃ which is an oxide.

LaFeO ₃ is orthoferrite having a perovskite structure and is used as a material for various sensors and solid oxide fuel cells. However, manufacture of oxide magnetic materials whose main phase is a ferrite phase having a hexagonal M-type magnetoplumbite structure, that is, ferrite calcined bodies and ferrite sintered bodies used for ferrite sintered magnets and ferrite bonded magnets, etc. There are no examples used in the method.

In addition, in the SrLaCo ferrite magnet and the CaLaCo ferrite magnet described above, when the orthoferrite containing La is generated, the saturation magnetization is lowered. Therefore, the magnet is manufactured under such a condition that the orthoferrite is not generated as much as possible. That is, in the field of ferrite magnets, it was thought that LaFeO ₃ should not be contained.

However, as a result of intensive studies by the inventors, even if LaFeO ₃ that was conventionally considered not to be contained is used as a raw material for La, the calcined body has a substantially hexagonal M-type magnetoplumbite structure. When a sintered magnet is manufactured using the calcined body, the ferrite phase becomes a single phase, and compared with the case where conventional La ₂ O ₃ or La (OH) ₃ is used as a raw material, _Br and H _k / The inventors have found that _HcJ is improved while maintaining _{HcJ, and} have _arrived at the present invention.

That is, the method for producing an oxide magnetic material according to the present invention is a method for producing an oxide magnetic material having a main phase of a ferrite phase having a hexagonal M-type magnetoplumbite structure containing La and Co. As a feature, LaFeO ₃ is used.

The oxide magnetic material is characterized in that the composition ratio of metal elements is represented by the following general formula (1) or (2).
General formula (1): A _1-x-a La _x Ca _a Fe _{2 n-y} Co _y
(However, the A element is Sr and / or Ba, and x, a and y representing the atomic ratio, and n representing the molar ratio are
0.05 ≦ x ≦ 0.4,
0.05 ≦ y ≦ 0.4,
0 ≦ a ≦ 0.3
0.5 ≦ 1-xa
3 ≦ n ≦ 6
It is a numerical value that satisfies )
Formula _{(2): Ca 1-x'} -b La x 'A b Fe 2n'-y' Co y '
(However, the element A is Sr and / or Ba, and x ′, b and y ′ representing the atomic ratio, and n ′ representing the molar ratio are
0.3 ≦ x ′ ≦ 0.7,
0 ≦ b <0.5,
0.1 ≦ y ′ ≦ 0.6,
0.2 ≦ 1-x′−b
3 ≦ n ′ ≦ 6
It is a numerical value that satisfies )

The production method of the present invention, without causing soaring raw material costs and process costs, it is possible to provide an oxide magnetic material with improved H _cJ while maintaining high B _r and H _{k /} H _cJ. By using the oxide magnetic material of the present invention, it is possible to provide automobile electrical parts and electrical equipment parts that are small, light, and highly efficient.

It is an X-ray diffraction pattern of the raw material 1 heat-processed at 700 to 1000 degreeC. It is an X-ray diffraction pattern of the raw material 1 heat-processed at 1100 degreeC-1300 degreeC. It is an X-ray diffraction pattern of the raw material 2 heat-processed at 700 to 1000 degreeC. It is an X-ray diffraction pattern of the raw material 2 heat-processed at 1100 degreeC-1300 degreeC. It is a figure which shows the SEM photograph of the raw material 1 heat-processed at 1200 degreeC. It is a figure which shows the SEM photograph of the raw material 2 heat-processed at 1200 degreeC. It is an X-ray diffraction pattern of calcined bodies A to D. It is a figure which shows the SEM photograph of the calcined body A. It is a figure which shows the SEM photograph of the calcined body B. It is a figure which shows the SEM photograph of the calcined body C. It is a figure which shows the SEM photograph of the calcined body D. It is an X-ray diffraction diagram of sintered magnets A to D. 2 is an X-ray diffraction diagram of a sintered magnet E. FIG. 3 is an X-ray diffraction diagram of a sintered magnet F. FIG. 3 is an X-ray diffraction diagram of a sintered magnet G. FIG. 2 is an X-ray diffraction diagram of a sintered magnet H. FIG. It is an X-ray diffraction diagram of sintered magnets I to K. It is an X-ray diffraction diagram of sintered magnets L to N.

[1] Oxide Magnetic Material An oxide magnetic material which is a target in the present invention is an oxide magnetic material containing a ferrite phase having a hexagonal M-type magnetoplumbite structure containing La and Co as a main phase. As long as the oxide magnetic material is an oxide magnetic material, the state, shape, and the like are not limited. For example, the state may be a calcined body or a sintered body (sintered magnet), and the shape may be a clinker after calcining, a powder of the calcined body, a molded body of the calcined body, It may be a powder of a sintered body.

  When the oxide magnetic material is a calcined body, the calcined body is composed of a ferrite phase having a hexagonal M-type magnetoplumbite structure.

  When the oxide magnetic material is a sintered body, the sintered body is composed of a ferrite phase having a hexagonal M-type magnetoplumbite structure, or a ferrite phase having a hexagonal M-type magnetoplumbite structure and It is comprised from compositions other than. The composition other than that is a composition or grain boundary phase present at the grain boundary of the ferrite phase, or a grain boundary phase present at the triple point portion of the grain boundary.

  Regardless of whether the oxide magnetic material is a calcined body or a sintered body, the main phase is a ferrite phase having a hexagonal M-type magnetoplumbite structure. The main phase refers to a phase occupying 50% by mass or more of the constituent phases constituting the calcined body or sintered body. In the oxide magnetic material according to the present invention, the ferrite phase having a hexagonal M-type magnetoplumbite structure accounts for 90 mass% or more in both the calcined body and the sintered body. The constituent phase other than the main phase is the above-mentioned composition or grain boundary phase, or the following different phase or impurity phase.

  “Having hexagonal M-type magnetoplumbite structure” means that when X-ray diffraction of a calcined ferrite body or a sintered ferrite body (ferrite sintered magnet) is measured under general conditions, the hexagonal M The X-ray diffraction pattern of the type magnetoplumbite structure is mainly observed. The presence of foreign phases (orthoferrite phase, spinel phase, etc.) and impurity phases observed in very small amounts (about 5% by mass or less) by X-ray diffraction or the like is allowed. A technique such as Rietveld analysis can be used for the quantification of heterogeneous phases from X-ray diffraction.

In the present invention, as an oxide magnetic material having a ferrite phase having a hexagonal M-type magnetoplumbite structure containing La and Co as a main phase, the composition ratio of metal elements is represented by the following general formula (1). So-called SrLaCo ferrite or so-called CaLaCo ferrite in which the composition ratio of the metal element is represented by the general formula (2) is preferable.
General formula (1): A _1-x-a La _x Ca _a Fe _{2 n-y} Co _y
Formula _{(2): Ca 1-x'} -b La x 'A b Fe 2n'-y' Co y '
Each will be described in detail below.

When the oxide magnetic material in the present invention is a sintered body (sintered magnet), a sintering aid such as CaCO ₃ or SiO ₂ is added in order to promote the sintering by generating a liquid phase during firing. To do. Most of the added CaCO ₃ , SiO _{2 and the} like form a grain boundary phase at the grain boundary of the ferrite compound phase. Therefore, the oxide magnetic material in the present invention includes a ferrite sintered magnet to which these sintering aids are added. When a sintering aid such as CaCO ₃ or SiO ₂ is added, the Ca content is relatively increased, and the content of other elements is relatively decreased due to the inclusion of Si. The SrLaCo ferrite and CaLaCo ferrite described in detail below are set in a range that takes into account the composition change due to the addition of such a sintering aid.

(A) SrLaCo Ferrite As the oxide magnetic material in the present invention, a so-called SrLaCo ferrite in which the composition ratio of metal elements is represented by the following general formula (1) is preferable.
General formula (1): A _1-x-a La _x Ca _a Fe _{2 n-y} Co _y
(However, the A element is Sr and / or Ba, and x, a and y representing the atomic ratio, and n representing the molar ratio are
0.05 ≦ x ≦ 0.4,
0.05 ≦ y ≦ 0.4,
0 ≦ a ≦ 0.3
0.5 ≦ 1-xa
3 ≦ n ≦ 6
It is a numerical value that satisfies )

  The element A is Sr and / or Ba. The content of element A (1-xa) is preferably 0.5 or more. That is, it is preferable that A element occupies 50% or more of A element + La + Ca. If the element A is less than 0.5, the contents of La and Ca are relatively increased and approach the CaLaCo ferrite, and the magnetic properties are improved depending on the Co content, but can be provided at a relatively low cost. This would impair the characteristics of SrLaCo ferrite.

The La content (x) is preferably in the range of 0.05 to 0.4. The content of La is not preferable because _{the B r} and _H k _{/ H cJ} is reduced is less than 0.05. Further, if the La content exceeds 0.4, the feature of SrLaCo ferrite that can be provided at a relatively low cost is impaired, which is not preferable. A part of La may be substituted with a rare earth element other than La. Further, rare earth elements mixed as inevitable impurities other than La can be tolerated.

The Ca content (a) is preferably 0.3 or less. If La increases similarly even if Ca exceeds 0.3, it will approach CaLaCo ferrite, and the magnetic properties will improve depending on the Co content, but it can be provided at a relatively low cost. The characteristics of will be impaired. On the other hand, when Ca exceeds 0.3 without increasing La, _Br is lowered, which is not preferable.

The Co content (y) is preferably in the range of 0.05 to 0.4. If the Co content is less than 0.05, the effect of improving the magnet properties by adding Co cannot be obtained. Secondary phase content of Co is rich in Co exceeds 0.4 (Co spinel phase) generated by _H cJ, with _{B r} and _H k _{/ H cJ} is reduced, be provided in a relatively inexpensive This is not preferable because the characteristics of the SrLaCo ferrite that can be formed are impaired. A part of Co (up to less than 50%) can be substituted with one or more of Zn, Ni, and Mn.

n is a value that reflects the molar ratio of (A + La + Ca) to (Fe + Co) and is represented by 2n = (Fe + Co) / (A + La + Ca). n is preferably from 3 to 6. If it is less than 3, the ratio of a nonmagnetic part will increase and _HcJ will fall large. More than 6 when _α-Fe 2 _{O 3} is left unreacted calcined _body, H cJ, _{undesirably B r} and _H k _{/ H cJ} is reduced.

(B) CaLaCo Ferrite As the oxide magnetic material in the present invention, a so-called CaLaCo ferrite in which the composition ratio of metal elements is represented by the following general formula (2) is preferable.
Formula _{(2): Ca 1-x'} -b La x 'A b Fe 2n'-y' Co y '
(However, the element A is Sr and / or Ba, and x ′, b and y ′ representing the atomic ratio, and n ′ representing the molar ratio are
0.3 ≦ x ′ ≦ 0.7,
0 ≦ b <0.5,
0.1 ≦ y ′ ≦ 0.6,
0.2 ≦ 1-x′−b
3 ≦ n ′ ≦ 6
It is a numerical value that satisfies )

The Ca content (1-x′-a) is preferably 0.2 or more. When the content of Ca is less than 0.2, the content is relatively increased La and A elements, especially La is not preferable because _{the B r} and _{H cJ} is reduced increases.

The content (x ′) of La is preferably 0.3 to 0.7. When the La content is less than 0.3, the Ca and A element contents are relatively increased. In particular, when the A element content is increased, it approaches SrLaCo ferrite, and the CaLaCo ferrite has superior magnetic properties compared to SrLaCo ferrite. there, it would impair the characteristics, Ca is not preferable because the B _r and H _cJ is reduced increases. The content of La is undesirable to exceed 0.7 when _{B r} and _H k _{/ H cJ} is reduced. A part of La may be substituted with a rare earth element other than La. Further, rare earth elements mixed as inevitable impurities other than La can be tolerated.

The element A is Sr and / or Ba. The content (b) of the A element is preferably less than 0.5. Even if it does not contain A element, the effect peculiar to CaLaCo ferrite is not impaired, but by adding A element, the crystal refinement and aspect ratio in the calcined body can be reduced, and H _cJ can be reduced. Further improvement can be achieved. When the content of the A element is 0.5 or more, it approaches SrLaCo ferrite, and the characteristics of CaLaCo ferrite, which is superior in magnetic properties as compared to SrLaCo ferrite, are impaired.

The Co content (y ′) is preferably 0.1 to 0.6. When the Co content is 0.1 or less, the effect of improving the magnet characteristics by adding Co cannot be obtained. Co content is hetero phases containing much Co exceeds 0.6 (Co spinel phase) generated by _H cJ, _{undesirably B r} and _H k _{/ H cJ} is reduced. A part of Co (up to less than 50%) can be substituted with one or more of Zn, Ni, and Mn.

n ′ is a value reflecting the molar ratio of (Ca + La + A) and (Fe + Co), and is represented by 2n ′ = (Fe + Co) / (Ca + La + A). n ′ is preferably 3 to 6. If it is less than 3, the ratio of the nonmagnetic portion increases, and the form of the calcined particles becomes excessively flat, and _HcJ is greatly reduced. More than 6 when _α-Fe 2 _{O 3} is left unreacted calcined _body, H cJ, _{undesirably B r} and _H k _{/ H cJ} is reduced.

[2] Method for Producing Oxide Magnetic Material A feature of the present invention resides in that LaFeO ₃ is used as a raw material for La in the method for producing an oxide magnetic material.

(A) Preparation LaFeO ₃ of LaFeO ₃ can be used those or accept the commercial product, produced by a known method. For example, as shown in the Examples described later, LaFeO ₃ can be prepared easily and inexpensively by heat-treating La (OH) ₃ and Fe ₂ O ₃ at a temperature of 900 ° C. or higher. Also, when preparing the LaFeO ₃ by heat treatment, or heat treatment body after the heat treatment need not be turned only LaFeO ₃ (LaFeO ₃ single phase), _La 2 _{O 3} and _Fe 2 _{O 3} is remained a small amount, It is used _{LaFeO 3 · zFe 2 O 3 (} z = 1~5) LaFeO 3 and _Fe 2 _O heat treated body consisting of two phases of ₃ such as actively formulated much _Fe 2 _{O 3,} present invention The effect of is not impaired.

(B) Method for producing calcined body Prepare raw material powder of LaFeO ₃ and other essential elements. For example, when producing SrLaCo ferrite, SrCO ₃ , LaFeO ₃ , Fe ₂ O ₃ , Co ₃ O ₄ , CaCO _{3 and the} like are prepared. In the case of producing CaLaCo ferrite, CaCO ₃ , LaFeO ₃ , SrCO ₃ , BaCO ₃ , Fe ₂ O ₃ , Co ₃ O _{4 and the} like are prepared. At this time, elements other than La may be not only oxides and carbonates as described above, but also hydroxides, nitrates, chlorides, and the like, and may be in a liquid state.

For example, as the element A compound, Sr and / or Ba carbonates, oxides, chlorides, and the like can be used. As the Ca compound, Ca carbonate, oxide, chloride and the like can be used. As the iron compound, iron oxide, iron hydroxide, iron chloride, mill scale and the like can be used. Examples of the Co compound include oxides such as CoO and Co ₃ O ₄ , hydroxides such as CoOOH, Co (OH) ₂ , and Co ₃ O ₄ .m ₁ H ₂ O (m ₁ is a positive number), CoCO ₃ like carbonates, and _{m 2 CoCO 3 · m 3 Co} (OH) 2 · m 4 H 2 O or the like basic carbonate _{(m 2, m 3, m} 4 are positive numbers) using can do.

As the La compound, not only LaFeO ₃ but also other La raw materials can be used in combination. However, when other La raw materials are used, it is desirable to make the amount used so that the effect of improving _HcJ by using LaFeO ₃ is not impaired. As other La raw materials, oxides such as La ₂ O ₃ , hydroxides such as La (OH) ₃ , carbonates such as La ₂ (CO ₃ ) ₃ · 8H ₂ O, and the like can be used. In order to reduce costs, mixed rare earth (La, Nd, Pr, Ce, etc.) oxides, hydroxides, carbonates, and the like can also be used.

Each raw material powder is weighed so as to have a target composition. In this case, so that the amount of Fe object by summing the Fe by Fe and _Fe 2 _{O 3} contained in LaFeO _3, to adjust the LaFeO ₃ and _Fe 2 _{O 3.}

The raw material powder of LaFeO ₃ and other essential elements may be added all at the time of raw material mixing and calcined, or part or all may be added after calcining. For example, when manufacturing a SrLaCo ferrite sintered magnet, SrCO ₃ , LaFeO ₃ and Fe ₂ O ₃ are blended, mixed and calcined, then Co ₃ O ₄ is added to the calcined body, and pulverized, molded and calcined. As a result, a SrLaCo ferrite sintered magnet can also be manufactured.

  The mixed raw material powder after weighing is mixed. Mixing may be either wet or dry. When the raw material powder is stirred together with a medium such as a steel ball, it can be mixed more uniformly. In the case of wet mixing, it is preferable to use water as a solvent. For the purpose of enhancing the dispersibility of the raw material powder, a known dispersant such as ammonium polycarboxylate or calcium gluconate may be used. The mixed raw material slurry is dehydrated to obtain a mixed raw material powder.

When mixing the mixed raw material powder, a compound containing B ₂ O ₃ , H ₃ BO ₃ or the like may be added as necessary to promote the reactivity during calcination. In particular the addition of _H 3 BO _{3 is} effective in improving the _{H cJ} and _{B r.} The amount of H ₃ BO ₃ added is preferably 0.3% by mass or less with respect to 100% by mass of the blended powder or calcined body. The most preferable value of the addition amount is around 0.2% by mass. H ₃ BO amount of ₃ to not obtained the effect of improving the _{B r} With less than 0.1 wt%, to the _{B r} many lower than 0.3 wt%. When manufacturing a sintered body, H ₃ BO ₃ has a function of controlling the shape and size of crystal grains during sintering. Therefore, after calcination (before fine pulverization or before sintering) And may be added both before and after calcination.

  By heating the mixed raw material powder using an electric furnace, a gas furnace or the like, a solid-phase reaction proceeds and a hexagonal M-type magnetoplumbite ferrite compound is formed. This process is called “calcination” and the resulting compound is called “calcination”.

  The calcination step is preferably performed in an atmosphere having an oxygen concentration of 5% or more. When the oxygen concentration is less than 5%, the solid-phase reaction hardly proceeds. A more preferable oxygen concentration is 20% or more.

  In the calcination step, a ferrite phase is formed by a solid-phase reaction as the temperature rises and is completed at about 1100 ° C. Below this temperature, unreacted hematite (iron oxide) and the like remain and the magnet properties deteriorate. In order to sufficiently exhibit the effects of the present invention, it is preferable to calcine at a temperature of 1100 ° C. or higher. On the other hand, if the calcining temperature exceeds 1450 ° C., crystal grains grow too much, and there is a risk that inconveniences such as requiring a long time for pulverization in the pulverization step may occur. Therefore, the calcination temperature is preferably 1100 to 1450 ° C. More preferably, it is 1200-1350 degreeC. The calcination time is preferably 0.5 to 5 hours.

(C) Manufacturing method of bonded magnet In order to pulverize the calcined body obtained by the above (b) to a required particle size and relieve crystal distortion, heat treatment is performed at a temperature of 700 to 1100 ° C. for about 0.1 to 3 hours. Apply. After the heat treatment, the powder is mixed with flexible rubber or hard plastic and then molded. The molding process may be performed by a known method such as injection molding, extrusion molding, or roll molding.

(D) Manufacturing method of sintered body (sintered magnet) The calcined body obtained by the above (b) is pulverized by a vibration mill, a ball mill and / or an attritor to obtain a pulverized powder. The pulverized powder preferably has an average particle size of about 0.4 to 0.8 μm (air permeation method). The pulverization step may be either dry pulverization or wet pulverization, but is preferably performed in combination.

In the pulverization step, 2% by mass or less of CaCO ₃ in terms of CaO and 2% by mass or less of SiO ₂ are added as sintering aids to 100% by mass of the calcined body. With this sintering aid, a liquid phase is generated during firing and the sintering can be promoted, and the _HcJ of the ferrite sintered magnet can be improved. CaCO _3, the SiO ₂ both added amount exceeds 2 mass% is not preferable because _{the B r} and _H k _{/ H cJ} is reduced. The preferred amount is, CaCO ₃ is 0.7 to 2.0 mass% in terms of CaO, SiO ₂ is 0.6 to 1.2 mass%.

Incidentally, SiO ₂ is most preferably added to the calcined body, it may be added to a portion of the total amount pre-calcination (during mixing of the raw material powder). By adding it before calcination, the crystal grain size during calcination can be controlled.

  In the wet pulverization, an aqueous dispersion medium such as water or various non-aqueous dispersion media (for example, organic solvents such as acetone, ethanol, xylene, etc.) can be used. By the wet pulverization, a slurry in which the solvent and the calcined body are mixed is generated. It is preferable to add 0.2 to 2% by mass of various known dispersants and surfactants in a solid content ratio to the slurry. The slurry after wet pulverization is preferably concentrated and kneaded.

In the pulverization step, additives such as Cr ₂ O ₃ , Al ₂ O ₃ , NH ₄ HCO _{3 and the} like may be added to the calcined body in order to improve the magnet characteristics in addition to the CaCO ₃ and SiO _2. it can. When adding these additives, 5 mass% or less is preferable.

  The pulverized slurry is press-molded in a magnetic field or without a magnetic field while removing the dispersion medium. By press molding in a magnetic field, the crystal orientation of the powder particles can be aligned (orientated), and the magnet characteristics can be greatly improved. Further, in order to improve the orientation, 0.01 to 1% by mass of a dispersant and a lubricant may be added. Moreover, you may concentrate a slurry before shaping | molding as needed. Concentration is preferably performed by centrifugation, filter press or the like.

  The molded body obtained by press molding is degreased if necessary and then fired. Firing is performed using an electric furnace, a gas furnace, or the like. Firing is preferably performed in an atmosphere having an oxygen concentration of 10% or more. If the oxygen concentration is less than 10%, abnormal grain growth and generation of a different phase are caused, and the magnet characteristics are deteriorated. The oxygen concentration is more preferably 20% or more, and most preferably 100%.

  The firing temperature is preferably 1150 ° C to 1250 ° C. The firing time is preferably 0.5 to 2 hours. The average crystal grain size of the sintered magnet obtained by the firing process is about 0.5 to 2 μm.

  After the firing step, a ferrite sintered magnet product is finally completed through known manufacturing processes such as a processing step, a cleaning step, and an inspection step.

Example 1
[Preparation of LaFeO ₃ ]
La raw material 1 weighed La (OH) ₃ and Fe ₂ O ₃ at 70.4% by mass: 29.6% by mass, and La (OH) ₃ and Fe ₂ O ₃ at 44.22% by mass: 55.78. La raw material 2 weighed in mass% was prepared. The raw material 1 has a target composition of LaFeO ₃ (LaFeO ₃ .zFe ₂ O ₃ , z = 0), and the raw material 2 has a target composition of LaFeO ₃ .Fe ₂ O ₃ (LaFeO ₃ .zFe ₂ O ₃ , z = 1). .

  Weighed raw material 1 and raw material 2 were each inserted into a ball mill, water was added as a solvent, and the mixture was rotated for 1 hour and mixed. The obtained raw material 1 and the raw material 2 were shape | molded, and the some molded object was produced. The molded body was heat-treated in the atmosphere at 700 ° C. to 1300 ° C. (100 ° C. pitch).

The X-ray diffraction results for each heat treatment temperature of the powder obtained by pulverizing the obtained heat treated body are shown in FIGS. 1 is a heat treatment body of raw material 1 at 700 ° C. to 1000 ° C., FIG. 2 is a heat treatment body of raw material 1 at 1100 ° C. to 1300 ° C., FIG. 3 is a heat treatment body of raw material 2 at 700 ° C. to 1000 ° C., and FIG. It is a X-ray-diffraction figure of the heat processing body of 1100 to 1300 degreeC. In the figure, ♦ indicates the diffraction line of LaFeO ₃ . In addition, diffraction lines existing near 26 °, 29 ° and 30 ° of 2θ are La ₂ O ₃ diffraction lines and exist at 24 °, 33 °, 36 ° and 49 ° of 2θ. The diffraction line to be shown is the diffraction line of Fe ₂ O ₃ .

As is clear from FIGS. 1 to 4, the diffraction lines of LaFeO ₃ are prominent at 900 ° C. or higher for both the raw materials 1 and 2. It can be seen that the raw material 1 is almost LaFeO ₃ single phase at 1200 ° C. or higher, and the raw material 2 is LaFeO ₃ and Fe ₂ O ₃ at 1000 ° C. or higher. Thus, a La raw material containing LaFeO ₃ such as the raw material 1 and the raw material 2 can be prepared by a relatively simple method of heat treatment at a temperature of 900 ° C. or higher.

  Moreover, the SEM photograph of the torn surface of the obtained heat processing body is shown in FIG.5 and FIG.6. FIG. 5 shows a 1200 ° C. heat treatment body of the raw material 1, and FIG. 6 shows a 1200 ° C. heat treatment body of the raw material 2.

[Production of SrLaCo ferrite calcined body (1)]
The heat-treated body at 900 ° C. of the raw material 1 was pulverized to prepare LaFeO ₃ powder as a La raw material. Formula _(1): in _{A 1-x-a La x} Ca a Fe 2n-y Co y, with Sr as the A element, x = 0.206, a = 0 , y = 0.145 and n = 5 The LaFeO ₃ powder, the SrCO ₃ powder, the Fe ₂ O ₃ powder and the Co ₃ O ₄ powder are blended so as to be 0.52 and 0.1% by mass of H ₃ BO _{3 with} respect to 100% by mass of the blended powder. and to prepare a mixed raw material powder was added 0.175% by weight of SiO _2. Water was added to this mixed raw material powder, mixed for 4 hours in a ball mill, dried, and then calcined in the atmosphere at 1300 ° C. for 3 hours to obtain calcined body A.

For comparison, calcined body B was obtained in the same manner except that La (OH) ₃ powder was used as the La raw material instead of LaFeO ₃ powder.

  The X-ray diffraction results of the obtained calcined bodies A and B are shown in FIG. In the figure, a circle indicates a diffraction line of a ferrite phase having a hexagonal M-type magnetoplumbite structure. In both of the calcined bodies A and B, the diffraction lines of the ferrite phase having a hexagonal M-type magnetoplumbite structure are remarkable, and the other diffraction lines are hardly seen. From this result, it can be seen that both the calcined bodies A and B are a single phase of a ferrite phase having a hexagonal M-type magnetoplumbite structure, and the ferrite phase is a main phase.

  Moreover, the SEM photograph of the obtained calcined body is shown in FIGS. 8 shows the calcined body A, and FIG. 9 shows the calcined body B.

[Production of SrLaCo ferrite sintered body (1)]
The calcined bodies A and B are roughly pulverized with a hammer mill to form a coarsely pulverized powder, and then CaCO ₃ is 0.34 mass% in terms of CaO with respect to 100% by mass of each calcined body coarsely pulverized powder. ₂ is mixed with 0.25% by mass, Co ₃ O ₄ is mixed with 0.4% by mass, and NH ₄ HCO ₃ is mixed with 0.3% by mass. Water is added and the mixture is finely pulverized with a ball mill for 30 hours. A finely pulverized powder was obtained. The average particle size of the finely pulverized powder was 0.6 μm (air permeation method).

The slurry-like finely pulverized powder obtained was mixed with 0.3% by mass of NH ₄ HCO ₃ and stirred. Then, while applying a magnetic field of about 1 T so that the pressurizing direction and the magnetic field direction were parallel, about 50 MPa It shape | molded, applying the pressure of and removing water. The obtained molded body was fired at 1200 ° C. for 1 hour in the air to obtain a sintered body (sintered magnet).

B _r , H _cJ and H _k / H _cJ (H _k is the value of J in the second quadrant of the J [magnetization strength] -H [magnetic field strength] curve of the obtained sintered magnet at room temperature. H value when B _r × 0.95) was measured. The results are shown in Table 1. The sintered magnet A (the present invention) is obtained by pulverizing, forming and firing the calcined body A, and the sintered magnet B (comparative example) is obtained by pulverizing, forming and firing the calcined body B.

As shown in Table 1, the sintered magnet A (the present invention) based on the calcined body A using the raw material 1 made of LaFeO ₃ is used as the calcined body B using the conventionally known La (OH) ₃ as a raw material. compared with the sintered magnet B (Comparative example) based, it can be seen _{that H cJ} of _{B r} and _H k _{/ H cJ} with little lowering is improved.

  Moreover, the X-ray-diffraction result of the obtained sintered magnets A and B is shown in FIG. In the figure, a circle indicates a diffraction line of a ferrite phase having a hexagonal M-type magnetoplumbite structure. In both of the sintered magnets A and B, the diffraction lines of the ferrite phase having a hexagonal M-type magnetoplumbite structure are remarkable, and the other diffraction lines are hardly seen. From this result, it can be seen that both the sintered magnets A and B have a main phase of a ferrite phase having a hexagonal M-type magnetoplumbite structure.

Example 2
[Production of CaLaCo ferrite calcined body]
The heat-treated body at 900 ° C. of the raw material 1 of Example 1 was pulverized to prepare LaFeO ₃ powder as a La raw material. Formula (2): _{'In, x' Ca 1-x'-} b La x 'A b Fe 2n'-y' Co y = 0.5, b = 0.075 (A element = Ba), y ' = 0.3 and n '= 5.3, the LaFeO ₃ powder, CaCO ₃ powder, BaCO ₃ powder, Fe ₂ O ₃ powder and Co ₃ O ₄ powder were blended, and the blended powder was 100% by mass. to prepare a mixed raw material powder was added _H 3 BO ₃ 0.1 wt% with respect to. Water was added to this mixed raw material powder, mixed for 4 hours in a ball mill, dried, and then calcined in the atmosphere at 1300 ° C. for 3 hours to obtain calcined body C.

For comparison, a calcined body D was obtained by the same method except that La (OH) ₃ powder was used instead of LaFeO ₃ powder as a La raw material.

  The X-ray diffraction results of the obtained calcined bodies C and D are shown in FIG. In the figure, a circle indicates a diffraction line of a ferrite phase having a hexagonal M-type magnetoplumbite structure. In both of the calcined bodies C and D, the diffraction lines of the ferrite phase having a hexagonal M-type magnetoplumbite structure are remarkable, and the other diffraction lines are hardly seen. From this result, it can be seen that both the calcined bodies C and D are a single phase of a ferrite phase having a hexagonal M-type magnetoplumbite structure, and the ferrite phase is a main phase.

  Moreover, the SEM photograph of the obtained calcined body is shown in FIG.10 and FIG.11. FIG. 10 shows the calcined body C, and FIG.

[Production of CaLaCo ferrite sintered body]
The calcined bodies C and D are coarsely pulverized with a hammer mill to form a coarsely pulverized powder, and then CaCO ₃ is converted to 0.48% by mass in terms of CaO, and 100% by mass of each calcined body coarsely pulverized powder. ₂ was mixed by 0.5% by mass and NH ₄ HCO ₃ was mixed by 0.4% by mass. Water was added and the mixture was finely pulverized with a ball mill for 30 hours to obtain a finely pulverized powder in the form of a slurry. The average particle size of the finely pulverized powder was 0.6 μm (air permeation method).

The slurry-like finely pulverized powder obtained was mixed with 0.3% by mass of NH ₄ HCO ₃ and stirred. Then, while applying a magnetic field of about 1 T so that the pressurizing direction and the magnetic field direction were parallel, about 50 MPa It shape | molded, applying the pressure of and removing water. The obtained molded body was fired at 1200 ° C. for 1 hour in the air to obtain a sintered body (sintered magnet).

B _r , H _cJ and H _k / H _cJ (H _k is the value of J in the second quadrant of the J [magnetization strength] -H [magnetic field strength] curve of the obtained sintered magnet at room temperature. H value when B _r × 0.95) was measured. The results are shown in Table 2. A sintered magnet C (the present invention) is obtained by pulverizing, forming and firing the calcined body C, and a sintered magnet D (comparative example) is obtained by pulverizing, forming and firing the calcined body D.

As shown in Table 2, the sintered magnet C (the present invention) based on the calcined body C using the raw material 1 made of LaFeO ₃ is used as the calcined body D using the conventionally known La (OH) ₃ as a raw material. compared with the sintered magnet D (Comparative example) based, it can be seen _{that H cJ} of _{B r} and _H k _{/ H cJ} with little lowering is improved.

  Moreover, the X-ray-diffraction result of the obtained sintered magnets C and D is shown in FIG. In the figure, a circle indicates a diffraction line of a ferrite phase having a hexagonal M-type magnetoplumbite structure. In both of the sintered magnets C and D, the diffraction lines of the ferrite phase having a hexagonal M-type magnetoplumbite structure are remarkable, and the other diffraction lines are hardly seen. From this result, it can be seen that both the sintered magnets C and D have a ferrite phase having a hexagonal M-type magnetoplumbite structure as a main phase.

Example 3
Except for preparing a LaFeO ₃ powder as a La raw material by pulverizing a heat treatment body at 1100 ° C. and 1300 ° C. in the raw material 1 of the target composition LaFeO ₃ (LaFeO ₃ .zFe ₂ O ₃ , z = 0) of Example 1. SrLaCo ferrite calcined bodies E and F were obtained in the same manner as in Example 1. Using the obtained calcined bodies E and F, a SrLaCo ferrite sintered body (sintered magnet) was obtained in the same manner as in Example 1.

B _r , H _cJ and H _k / H _cJ (H _k is the value of J in the second quadrant of the J [magnetization strength] -H [magnetic field strength] curve of the obtained sintered magnet at room temperature. H value when B _r × 0.95) was measured. The results are shown in Table 3. A sintered magnet E (the present invention) is obtained by pulverizing, forming and firing the calcined body E, and a sintered magnet F (the present invention) is obtained by pulverizing, forming and firing the calcined body F. For comparison, the magnet characteristics of the sintered magnet B (comparative example) based on the calcined body B using La (OH) ₃ powder as the La raw material of Example 1 are also shown.

As shown in Table 3, based on calcined bodies E and F using heat treated bodies of 1100 ° C. and 1300 ° C. in raw material 1 of the target composition LaFeO ₃ (LaFeO ₃ .zFe ₂ O ₃ , z = 0) of Example 1 sintered magnet E and F (invention) compared with La (OH) sintered magnet B (comparative example) based on the calcined B using ₃ as the raw materials conventionally known, little lowering the B _r It can be seen that H _cJ and H _k / H _cJ are improved.

  Moreover, the X-ray diffraction result of the sintered magnet E is shown in FIG. 13, and the X-ray diffraction result of the sintered magnet F is shown in FIG. In the figure, a circle indicates a diffraction line of a ferrite phase having a hexagonal M-type magnetoplumbite structure. In both of the sintered magnets E and F, the diffraction lines of the ferrite phase having a hexagonal M-type magnetoplumbite structure are remarkable, and the other diffraction lines are hardly seen. From this result, it can be seen that both the sintered magnets E and F have a main phase of a ferrite phase having a hexagonal M-type magnetoplumbite structure.

As is apparent from the results of Example 1 and Example 3, a heat-treated body obtained by heat-treating a raw material 1 having a target composition of LaFeO ₃ (LaFeO ₃ .zFe ₂ O ₃ , z = 0) at 900 ° C. or higher is used as a La raw material. SrLaCo ferrite sintered magnets (sintered magnets A, E, and F) based on the SrLaCo ferrite calcined bodies (calcined bodies A, E, and F) used here are all made of La (OH) ₃ known as a raw material. It can be seen that H _cJ is improved while maintaining high B _r and H _k / H _cJ as compared to SrLaCo ferrite sintered magnet B (comparative example) based on SrLaCo ferrite calcined body B.

Example 4
Except for preparing a LaFeO ₃ powder as a La raw material by pulverizing a heat treatment body at 1100 ° C. and 1300 ° C. in the raw material 1 of the target composition LaFeO ₃ (LaFeO ₃ .zFe ₂ O ₃ , z = 0) of Example 1. CaLaCo ferrite calcined bodies G and H were obtained in the same manner as in Example 2. A CaLaCo ferrite sintered body (sintered magnet) was obtained by the same method as in Example 2 using the obtained calcined bodies G and H.

B _r , H _cJ and H _k / H _cJ (H _k is the value of J in the second quadrant of the J [magnetization strength] -H [magnetic field strength] curve of the obtained sintered magnet at room temperature. H value when B _r × 0.95) was measured. The results are shown in Table 4. A sintered magnet G (the present invention) is obtained by pulverizing, forming and firing the calcined body G, and a sintered magnet H (the present invention) is obtained by pulverizing, forming and firing the calcined body H. For comparison, the magnetic characteristics of the sintered magnet D (comparative example) based on the calcined body D using La (OH) ₃ powder as the La raw material of Example 2 are also shown.

As shown in Table 4, based on calcined bodies G and H using heat treated bodies of 1100 ° C. and 1300 ° C. in the raw material 1 of the target composition LaFeO ₃ (LaFeO ₃ .zFe ₂ O ₃ , z = 0) of Example 1 sintered magnet G and H (invention) compared with La known conventionally (OH) sintered magnet D (Comparative example) based on the calcined D using ₃ as a raw material, without lowering the B _r It can be seen that H _cJ and H _k / H _cJ are improved.

  15 shows the X-ray diffraction result of the sintered magnet G, and FIG. 16 shows the X-ray diffraction result of the sintered magnet H. In the figure, a circle indicates a diffraction line of a ferrite phase having a hexagonal M-type magnetoplumbite structure. In both of the sintered magnets G and H, the diffraction lines of the ferrite phase having a hexagonal M-type magnetoplumbite structure are remarkable, and the other diffraction lines are hardly seen. From this result, it can be seen that both the sintered magnets G and H have a main phase of a ferrite phase having a hexagonal M-type magnetoplumbite structure.

As is apparent from the results of Examples 2 and ₃ , a heat-treated body obtained by heat-treating a raw material 1 having a target composition of LaFeO ₃ (LaFeO ₃ .zFe ₂ O ₃ , z = 0) at 900 ° C. or higher is used as the La raw material. CaLaCo ferrite sintered magnets (sintered magnets C, G, and H) based on the CaLaCo ferrite calcined bodies (calcined bodies C, G, and H) that have been conventionally used are La (OH) ₃ as a raw material. compared to have a CaLaCo ferrite calcined body CaLaCo ferrite sintered magnet B based on B (Comparative example), _{H cJ} while maintaining high _{B r} and _H k _{/ H cJ} that is improved understood.

Example 5
LaFeO which becomes the La raw material by pulverizing the 900 ° C., 1100 ° C. and 1300 ° C. heat treatment bodies in the raw material 2 of the target composition LaFeO ₃ .Fe ₂ O ₃ (LaFeO ₃ .zFe ₂ O ₃ , z = 1) of Example 1 SrLaCo ferrite calcined bodies I, J and K were obtained by the same method as in Example 1 except that ₃ · Fe ₂ O ₃ powder was prepared. A SrLaCo ferrite sintered body (sintered magnet) was obtained by the same method as in Example 1 using the obtained calcined bodies I, J, and K.

B _r , H _cJ and H _k / H _cJ (H _k is the value of J in the second quadrant of the J [magnetization strength] -H [magnetic field strength] curve of the obtained sintered magnet at room temperature. H value when B _r × 0.95) was measured. The results are shown in Table 5. Crushed, molded and fired calcined body I is sintered magnet I (the present invention), and calcined body J is ground, molded and fired is sintered magnet J (the present invention) and calcined body K. The sintered magnet K (the present invention) is formed and fired. For comparison, the magnet characteristics of the sintered magnet B (comparative example) based on the calcined body B using La (OH) ₃ powder as the La raw material of Example 1 are also shown.

As shown in Table 5, heat treatment bodies at 900 ° C., 1100 ° C., and 1300 ° C. in the raw material 2 of the target composition LaFeO ₃ .Fe ₂ O ₃ (LaFeO ₃ .zFe ₂ O ₃ , z = 1) of Example 1 were used. Sintered magnets I, J, and K based on calcined bodies I, J, and K (invention) are sintered magnets B based on calcined body B using La (OH) ₃ known as a raw material (comparison). compared to example), it can be seen _{that H cJ} and _H k _{/ H cJ} of _{B r} with little lowering is improved.

  Moreover, the X-ray-diffraction result of sintered magnet I, J, and K is shown in FIG. In the figure, a circle indicates a diffraction line of a ferrite phase having a hexagonal M-type magnetoplumbite structure. In all of the sintered magnets I, J, and K, the diffraction line of the ferrite phase having a hexagonal M-type magnetoplumbite structure is remarkable, and the other diffraction lines are hardly seen. From this result, it can be seen that all of the sintered magnets I, J, and K have a ferrite phase having a hexagonal M-type magnetoplumbite structure as a main phase.

Thus, a SrLaCo ferrite calcined body using a heat treated body obtained by heat-treating a raw material 2 having a target composition of LaFeO ₃ .Fe ₂ O ₃ (LaFeO ₃ .zFe ₂ O ₃ , z = 1) at 900 ° C. or more as a La raw material. SrLaCo ferrite sintered magnets (sintered magnets I, J and K) based on (calcined bodies I, J and K) are all SrLaCo ferrite calcined bodies using La (OH) ₃ known as a raw material. Compared to the SrLaCo ferrite sintered magnet B (comparative example) based on B, it can be seen that H _cJ is improved while maintaining high B _r and H _k / H _cJ .

Example 6
LaFeO which becomes the La raw material by pulverizing the 900 ° C., 1100 ° C. and 1300 ° C. heat treatment bodies in the raw material 2 of the target composition LaFeO ₃ .Fe ₂ O ₃ (LaFeO ₃ .zFe ₂ O ₃ , z = 1) of Example 1 CaLaCo ferrite calcined bodies L, M and N were obtained in the same manner as in Example 2 except that ₃ · Fe ₂ O ₃ powder was prepared. Using the obtained calcined bodies L, M and N, a CaLaCo ferrite sintered body (sintered magnet) was obtained in the same manner as in Example 2.

B _r , H _cJ and H _k / H _cJ (H _k is the value of J in the second quadrant of the J [magnetization strength] -H [magnetic field strength] curve of the obtained sintered magnet at room temperature. H value when B _r × 0.95) was measured. The results are shown in Table 6. Crushed, molded and fired calcined body L is sintered magnet L (the present invention), and calcined body M is ground, molded and fired is sintered magnet M (the present invention) and calcined body N is ground. The sintered and magnet N (the present invention) is formed and fired. For comparison, the magnetic characteristics of the sintered magnet D (comparative example) based on the calcined body D using La (OH) ₃ powder as the La raw material of Example 2 are also shown.

As shown in Table 6, the heat treatment bodies at 900 ° C., 1100 ° C. and 1300 ° C. in the raw material 2 of the target composition LaFeO ₃ .Fe ₂ O ₃ (LaFeO ₃ .zFe ₂ O ₃ , z = 1) of Example 1 were used. The sintered magnets L, M, and N (invention) based on the calcined bodies L, M, and N are the sintered magnets D (comparative) based on the calcined body D that uses the conventionally known La (OH) ₃ as a raw material. compared to example), it can be seen _{that H cJ} and _H k _{/ H cJ} of _{B r} with little lowering is improved. In particular, the improvement of _HcJ is remarkable.

  Moreover, the X-ray-diffraction result of the sintered magnets L, M, and N is shown in FIG. In the figure, a circle indicates a diffraction line of a ferrite phase having a hexagonal M-type magnetoplumbite structure. In all of the sintered magnets L, M, and N, the diffraction lines of the ferrite phase having a hexagonal M-type magnetoplumbite structure are remarkable, and the other diffraction lines are hardly seen. From this result, it can be seen that all of the sintered magnets L, M, and N have a ferrite phase having a hexagonal M-type magnetoplumbite structure as a main phase.

Thus, a CaLaCo ferrite calcined body using as a La raw material a heat-treated body obtained by heat-treating a raw material 2 having a target composition of LaFeO ₃ .Fe ₂ O ₃ (LaFeO ₃ .zFe ₂ O ₃ , z = 1) at 900 ° C. or higher. CaLaCo ferrite sintered magnets (sintered magnets L, M and N) based on (calcined bodies L, M and N) are all CaLaCo ferrite calcined bodies using La (OH) ₃ which has been conventionally known as a raw material. compared to CaLaCo ferrite sintered magnet D (Comparative example) based on D, _{H cJ} while maintaining high _{B r} and _H k _{/ H cJ} that is improved understood.

Oxide magnetic material obtained by the manufacturing method of the oxide magnetic material of the present invention, without causing soaring raw material costs and process costs, H _cJ is improved while maintaining high B _r and H _{k /} H _cJ Therefore, it is most suitable for applications such as electric parts for automobiles and parts for electric equipment that have been made smaller, lighter and more efficient.

Claims (2)

In a method for producing an oxide magnetic material containing a ferrite phase having a hexagonal M-type magnetoplumbite structure containing La and Co as a main phase,
A method for producing an oxide magnetic material, wherein LaFeO ₃ is used as a raw material of La. 2. The method for producing an oxide magnetic material according to claim 1, wherein the composition ratio of the metal element is represented by the following general formula (1) or (2).
General formula (1): A _1-x-a La _x Ca _a Fe _{2 n-y} Co _y
(However, the A element is Sr and / or Ba, and x, a and y representing the atomic ratio, and n representing the molar ratio are
0.05 ≦ x ≦ 0.4,
0.05 ≦ y ≦ 0.4,
0 ≦ a ≦ 0.3
0.5 ≦ 1-xa
3 ≦ n ≦ 6
It is a numerical value that satisfies )
Formula _{(2): Ca 1-x'} -b La x 'A b Fe 2n'-y' Co y '
(However, the element A is Sr and / or Ba, and x ′, b and y ′ representing the atomic ratio, and n ′ representing the molar ratio are
0.3 ≦ x ′ ≦ 0.7,
0 ≦ b <0.5,
0.1 ≦ y ′ ≦ 0.6,
0.2 ≦ 1-x′−b
3 ≦ n ′ ≦ 6
It is a numerical value that satisfies )