WO2011001831A1 - フェライト焼結磁石の製造方法及びフェライト焼結磁石 - Google Patents
フェライト焼結磁石の製造方法及びフェライト焼結磁石 Download PDFInfo
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- WO2011001831A1 WO2011001831A1 PCT/JP2010/060280 JP2010060280W WO2011001831A1 WO 2011001831 A1 WO2011001831 A1 WO 2011001831A1 JP 2010060280 W JP2010060280 W JP 2010060280W WO 2011001831 A1 WO2011001831 A1 WO 2011001831A1
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Definitions
- the present invention relates to a method of manufacturing a ferrite sintered magnet and a ferrite sintered magnet.
- Ferrite sintered magnets are used in various applications such as various motors, generators, and speakers.
- Sr ferrite (SrFe 12 O 19 ) and Ba ferrite (BaFe 12 O 19 ) having a hexagonal M-type magnetoplumbite structure are known.
- These ferrite sintered magnets are produced relatively inexpensively by powder metallurgy, using iron oxide and carbonates of strontium (Sr) or barium (Ba) as raw materials.
- Sr ferrites described in JP-A-10-149910 and JP-A-11-154604 in which part of Sr is substituted with a rare earth element such as La and part of Fe is substituted with Co or the like (hereinafter referred to as "SrLaCo ferrite") ) Is widely used for various applications in place of conventional Sr ferrites and Ba ferrites because it is excellent in magnet characteristics, but further improvement of magnet characteristics is also desired.
- Ca ferrite is also known as a ferrite sintered magnet, in addition to the above-mentioned Sr ferrite and Ba ferrite. It is known that Ca ferrite has a stable structure represented by a composition formula of CaO-Fe 2 O 3 or CaO 2 -Fe 2 O 3 and forms hexagonal ferrite by adding La. However, the obtained magnet characteristics were comparable to those of the conventional Ba ferrite and were not sufficiently high.
- Japanese Patent No. 3181559 substitutes a part of Ca with a rare earth element such as La in order to improve the residual magnetic flux density B r and the coercivity H cJ of Ca ferrite and to improve the temperature characteristics of the coercivity H cJ ,
- a Ca ferrite (hereinafter referred to as "CaLaCo ferrite") having an anisotropic magnetic field HA of 20 kOe or more in which a part of Fe is replaced by Co etc., and the anisotropic magnetic field HA is a Sr ferrite It is stated that the value is 10% or more higher than that.
- CaLaCo ferrite according to Patent No. 3181559 although an anisotropic magnetic field H A in excess of SrLaCo ferrite, B r and H cJ are comparable to SrLaCo ferrite, while the squareness ratio is very poor It can not satisfy high coercivity and high squareness ratio, and has not been applied to various applications such as motors.
- JP 2007-123511 proposes a method of improving the H cJ while maintaining the B r.
- a ferrite sintered magnet is (1) a compounding step of compounding and mixing iron oxide as a raw material and a carbonate of Sr or Ba and the like, and (2) calcinating the mixed raw material to obtain a calcined body Calcining step, (3) pulverizing the calcined body to obtain a powder, (4) shaping the powder to obtain a compact, (5) firing the compact to obtain a sintered body It is manufactured by the process.
- 2007-123511 discloses a method in which a pulverizing step is constituted by a first pulverizing step, a powder heat treatment step and a second pulverizing step, and crystals having a particle diameter of 1.1 ⁇ m or less by this method The ratio of the number of is 95% or more, thereby improving H cJ .
- Japanese Patent Application Laid-Open No. 2006-104050 proposes a CaLaCo ferrite in which the molar ratio of each constituent element and the value of n are optimized, and La and Co are contained at a specific ratio
- WO 2007/06057 No. proposes a CaLaCo ferrite in which a part of Ca is substituted by La and Ba
- WO 2007/077811 proposes a CaLaCo ferrite in which a part of Ca is substituted by La and Sr.
- Japanese Patent Application Laid-Open Nos. 2008-137879 and International Publication No. 2008/105449 adopt a technology that improves HcJ by adopting the grinding process described in Japanese Patent Application Laid-Open No. 2007-123511 in the manufacturing process of CaLaCo ferrite. It is disclosed.
- CaLaCo ferrite according to 2008-137879 Patent and WO 2008/105449 Patent although improvement in H cJ are achieved, as in the JP 2007-123511, the raw material costs and process costs Double cost increase, and can not meet the price requirements in the market.
- H cJ it is effective to increase the addition amount of the sintering aid or to increase the addition ratio of SiO 2 compared to CaCO 3 , but the increase of the nonmagnetic component and the sinterability lowered by reduced B r of, squareness ratio H k / H cJ [H k is, J in the second quadrant of the (magnetization magnitude) -H (field strength) curve, J is 0.95B r It is inevitable to reduce the value of H at the value position.
- WO 2007/06057 states that it is preferable to add 0.2 to 1.5% by mass (0.112 to 0.84% by mass in terms of CaO) of CaCO 3 and 0.1 to 1.5% by mass of SiO 2 at the time of pulverizing the calcined body.
- JP-A No. 2008-137879 describes that it is preferable to add 1.35 mass% or less of SiO 2 to the sintered material.
- an object of the present invention without a concomitant increase in raw material costs and process costs, and allows thinner by improving significantly the H cJ while maintaining high B r and squareness ratio H k / H cJ It is an object of the present invention to provide a CaLaCo ferrite sintered magnet and a manufacturing method capable of manufacturing the ferrite sintered magnet inexpensively.
- the inventors focused on the sintering aid added in the pulverizing step, and in CaLaCo ferrite, when (a) more than 1% by mass of SiO 2 was added as a sintering aid the H cJ is specifically improved, (b) this time, by the addition of 1 mass% or more CaCO 3 in accordance with the added amount of SiO 2, preventing a decrease in B r and H k / H cJ as much as possible may be found a result, it was not obtained so far, the ferrite sintered magnet having maintaining high B r and H k / H cJ and high H cJ obtained (c), conceived the present invention did.
- H cJ when adding SiO 2 in excess of 1% by mass is a phenomenon unique to CaLaCo ferrite, and the SrLaCo ferrites described in JP-A-10-149910 and JP-A-11-154604 are as each more than 1 wt% addition of SiO 2 and CaCO 3, improvement in H cJ significantly B r and H k / H cJ is reduced on small (see example 3 below).
- the HcJ of the CaLaCo ferrite magnet having an atomic ratio of Co of 0.3 described in the examples of JP-A-2006-104050, WO 2007/060757 and JP-A- 2008-137879 is as high as 400 kA / It is about m (about 5 kOe).
- HcJ of about 400 kA / m is also obtained by SrLaCo ferrite (Japanese Patent Laid-Open No. 2007-123511, the atomic ratio of Co is 0.2).
- JP 2006-104050 the CaLaCo ferrite magnet according to an embodiment of WO 2007/060757 and JP 2008-137879, the anisotropic magnetic field H A is applied to higher than SrLaCo ferrite I not, H cJ is approximately equivalent to the SrLaCo ferrite, not improved to a level that H cJ is expected, originally of potential material is not sufficiently exhibited.
- CaLaCo ferrite peculiar phenomenon that the addition of SiO 2 H cJ is improved specifically exceed 1% by weight are those innovative approaches to material intrinsic potential.
- the method of the present invention for producing a ferrite sintered magnet having a ferrite phase having a hexagonal M-type magnetoplumbite structure and a grain boundary phase essentially containing Si, Ca, R element containing at least one of rare earth elements and essentially containing La, A element containing Ba and / or Sr, Fe and Co as essential elements, metallic elements of Ca, R, A, Fe and Co
- the composition ratio is General formula Ca 1-xy R x A y Fe 2 n -z Co z Represented by 1-xy, x, y, z representing atomic ratio of Ca, R element, A element and Co, and n representing molar ratio respectively 0.3 ⁇ 1-xy ⁇ 0.65, 0.2 ⁇ x ⁇ 0.65, 0 ⁇ y ⁇ 0.2, 0.03 ⁇ z ⁇ 0.65, and 4 ⁇ n ⁇ 7
- the amount of SiO 2 added is preferably 1.1 to 1.6% by mass.
- the amount of CaO added is preferably 1.2 to 2% by mass.
- the 1-xy, x, y, z and n are 0.35 ⁇ 1-xy ⁇ 0.55, 0.4 ⁇ x ⁇ 0.6, 0 ⁇ y ⁇ 0.15, 0.1 ⁇ z ⁇ 0.4, and 4.5 ⁇ n ⁇ 6 Is preferred.
- the 1-xy, x, y, z and n are 0.42 ⁇ 1-xy ⁇ 0.5, 0.45 ⁇ x ⁇ 0.55, 0 ⁇ y ⁇ 0.08, 0.2 ⁇ z ⁇ 0.3, and 4.8 ⁇ n ⁇ 5.2 Is preferred.
- the pulverizing step includes a first pulverizing step, a step of heat-treating the powder obtained by the first pulverizing step, and a second pulverizing step of pulverizing the heat-treated powder again. It is preferable to consist of
- the sintered ferrite magnet of the present invention contains Ca, at least one of rare earth elements, an R element essentially containing La, an A element which is Ba and / or Sr, Fe and Co as essential elements, Ca, R,
- the composition ratio of metal elements of A, Fe and Co is General formula Ca 1-xy R x A y Fe 2 n -z Co z Represented by 1-xy, x, y, z representing atomic ratio of Ca, R element, A element and Co, and n representing molar ratio respectively 0.3 ⁇ 1-xy ⁇ 0.65, 0.2 ⁇ x ⁇ 0.65, 0 ⁇ y ⁇ 0.2, 0.03 ⁇ z ⁇ 0.65, and 4 ⁇ n ⁇ 7
- the content of Si is preferably 1.1 to 1.6% by mass in terms of SiO 2 with respect to the entire ferrite sintered magnet.
- the 1-xy, x, y, z and n are 0.35 ⁇ 1-xy ⁇ 0.55, 0.4 ⁇ x ⁇ 0.6, 0 ⁇ y ⁇ 0.15, 0.1 ⁇ z ⁇ 0.4, and 4.5 ⁇ n ⁇ 6 Is preferred.
- the 1-xy, x, y, z and n are 0.42 ⁇ 1-xy ⁇ 0.5, 0.45 ⁇ x ⁇ 0.55, 0 ⁇ y ⁇ 0.08, 0.2 ⁇ z ⁇ 0.3, and 4.8 ⁇ n ⁇ 5.2 Is preferred.
- Production method of the present invention may be reduced than the conventional amounts of essential rare and expensive Co and La in CaLaCo ferrite, significantly while H cJ maintaining high B r and squareness ratio H k / H cJ Since it can be improved, it is possible to provide a CaLaCo ferrite magnet excellent in economy. Further, the CaLaCo ferrite magnet obtained by the manufacturing method of the present invention does not cause demagnetization due to the demagnetizing field generated when the thickness is reduced. Therefore, the ferrite sintered magnet of the present invention can provide various types of motors that are reduced in size, weight and efficiency, electric parts for automobiles such as generators and speakers, parts for electric devices, and the like.
- FIG. 15 is a graph showing the relationship between CaO / SiO 2 and coercivity H cJ of the ferrite sintered magnet of Example 4.
- FIG. It is a graph showing a relationship between ferrite sintered amount of SiO 2 of sintered magnets with residual magnetic flux density B r of Example 5.
- 18 is a graph showing the relationship between the amount of SiO 2 added and the coercive force H cJ of the ferrite sintered magnet of Example 5. It is a graph showing the relationship between the mixing amount and the squareness ratio H k / H cJ of SiO 2 in the sintered ferrite magnets of Example 5.
- the ferrite-sintered magnet according to the present invention contains Ca, at least one of rare earth elements, and essentially R element containing La, element A, which is Ba and / or Sr, Fe and Co.
- the composition ratio of the metal elements of Ca, R, A, Fe and Co as elements is It is represented by the general formula Ca 1 -xy R x A y Fe 2 n -z Co z 1-xy, x, y, z representing atomic ratio of Ca, R element, A element and Co, and n representing molar ratio respectively 0.3 ⁇ 1-xy ⁇ 0.65, 0.2 ⁇ x ⁇ 0.65, 0 ⁇ y ⁇ 0.2, 0.03 ⁇ z ⁇ 0.65, and 4 ⁇ n ⁇ 7
- the content (1-xy) of Ca is 0.3 ⁇ 1-xy ⁇ 0.65.
- Ca is less than 0.3, R element and element A becomes relatively large is not preferable because the B r and H k / H cJ is reduced.
- R element and element A becomes relatively small, undesirably B r and H k / H cJ is reduced.
- a preferred range of 1-xy is 0.35 ⁇ 1-xy ⁇ 0.55, and a more preferred range is 0.42 ⁇ 1-xy ⁇ 0.5.
- the R element is at least one of rare earth elements and essentially contains La.
- the proportion of La in the R element is preferably 50 atomic% or more, more preferably 70 atomic% or more, and La alone (however, unavoidable impurities are acceptable) Is most preferred.
- La is most likely to form a solid solution in the M phase, so the larger the ratio of La, the larger the improvement effect of the magnetic characteristics.
- the content (x) of the R element is 0.2 ⁇ x ⁇ 0.65. When x is less than 0.2 and more than 0.65, B r and H k / H cJ decrease.
- a preferred range of x is 0.4 ⁇ x ⁇ 0.6, and a more preferred range is 0.45 ⁇ x ⁇ 0.55.
- the A element is Ba and / or Sr.
- the content (y) of the element A is 0 ⁇ y ⁇ 0.2.
- a preferable range of y is 0 ⁇ y ⁇ 0.15, and a more preferable range is 0 ⁇ y ⁇ 0.08.
- the content (z) of Co is 0.03 ⁇ z ⁇ 0.65. If z is less than 0.03, the effect of improving the magnetic properties by the addition of Co can not be obtained. In addition, since unreacted ⁇ -Fe 2 O 3 remains in the calcined body, slurry leakage occurs from the cavity of the mold during wet molding. When z exceeds 0.65, a hetero phase containing a large amount of Co is generated, and the magnetic properties are significantly reduced.
- a preferred range of z is 0.1 ⁇ z ⁇ 0.4, and a more preferred range is 0.2 ⁇ z ⁇ 0.3.
- Co can also be partially substituted by at least one selected from Zn, Ni and Mn.
- Zn, Ni and Mn the manufacturing cost can be reduced without deteriorating the magnetic properties.
- H cJ is slightly lowered, thereby improving the B r.
- the total substitution amount of Zn, Ni and Mn is preferably 50% or less of Co in molar ratio.
- H cJ In CaLaCo ferrite, essentially H cJ is improved with increasing Co and La.
- Co and La are classified as rare metals (rare metals), and because they are rare and expensive metals, it is desirable to reduce their content as much as possible in order to save resources or reduce the cost of ferrite sintered magnets.
- Be According to the present invention it is possible to significantly improve the H cJ while maintaining high B r and squareness ratio H k / H cJ, when providing a magnet of the same H cJ as conventional CaLaCo ferrite sintered magnet , Co and La contents can be reduced.
- the molar ratio n is preferably 4 ⁇ n ⁇ 7.
- n is less than 4, the ratio of the nonmagnetic portion increases, and the shape of the calcined particles becomes excessively flat, and the HcJ is significantly reduced.
- n exceeds 7 unreacted ⁇ -Fe 2 O 3 remains in the calcined body, and slurry leakage occurs from the cavity of the mold during wet molding.
- a preferred range of n is 4.5 ⁇ n ⁇ 6, and a more preferred range is 4.8 ⁇ z ⁇ 5.2.
- Si is an essential element and contains more than 1% by mass and 1.8% by mass or less in terms of SiO 2 with respect to the entire magnet. It is preferable to add Si as SiO 2 to the ferrite calcined body, and the amount of SiO 2 to be added is more than 1% by mass and preferably 1.8% by mass or less with respect to 100% by mass of the calcined body. That is, SiO 2 added to the calcined body is basically contained as it is also in the sintered magnet. However, it may flow out slightly in the pulverizing step or the forming step, and the content in the sintered magnet may be smaller than the amount added to the calcined body. Si basically forms a grain boundary phase and is not contained in the ferrite phase having a hexagonal M-type magnetoplumbite structure. A preferred range of Si is 1.1 to 1.6% by mass (in terms of SiO 2 ).
- the molar ratio x / z of R element to Co is preferably 0.73 ⁇ x / z ⁇ 15.62.
- a more preferable range is 1 ⁇ x / z ⁇ 3, and a most preferable range is 1.2 ⁇ x / z ⁇ 2.
- the ferrite sintered magnet of the present invention, or the calcined body according to the present invention has a ferrite phase having a hexagonal M-type magnetoplumbite structure.
- “having a hexagonal M-type magnetoplumbite structure” means a hexagonal M-type magnetoplumbite structure when X-ray diffraction of a ferrite sintered magnet or a calcined body is measured under a general condition.
- the X-ray diffraction pattern of is mainly observed.
- the presence of a foreign phase (orthoferrite phase, spinel phase, etc.) or an impurity phase observed in a very small amount (about 5% by mass or less) by X-ray diffraction or the like is acceptable.
- a method such as Rietveld analysis can be used for the determination of the different phase from X-ray diffraction.
- the ferrite sintered magnet of the present invention essentially has a ferrite phase having the hexagonal M-type magnetoplumbite structure and a grain boundary phase which contains Si essentially. Since it is difficult to observe the grain boundary phase with an X-ray diffraction pattern, it is preferable to confirm with a transmission electron microscope or the like.
- the ferrite phase in the ferrite calcined body and the ferrite phase in the ferrite sintered magnet both have a hexagonal M-type magnetoplumbite structure and are basically the same.
- a ferrite phase in advance for achieving crystal orientation at the time of forming and controlling the structure at the time of sintering, and the presence of the grain boundary phase is not limited.
- a grain boundary phase containing a ferrite phase as a main component and additionally containing Si essential for structure control and densification at the time of sintering is required.
- the coercivity H cJ is 450 kA / m or more, the residual magnetic flux density B r is 0.4 T or more, the squareness H k / H cJ 80 %, And by selecting a more preferable range, the coercive force H cJ is 460 kA / m or more, the residual magnetic flux density B r is 0.44 T or more, and the squareness ratio H k / H cJ is 80%. It has the above-mentioned magnet characteristic.
- a ferrite sintered magnet is a step of preparing a calcined ferrite body, a step of pulverizing the calcined body to obtain a powder, and a step of molding the powder to obtain a compact And manufacturing the sintered body by a sintering process to obtain a sintered body.
- the coercivity H of the sintered magnet is obtained by adding more than 1% by mass and less than 1.8% by mass of SiO 2 with respect to 100% by mass of the calcined body to the calcined body before the pulverizing step. cJ can be significantly improved.
- the ferrite calcined body contains Ca, an R element which is at least one of rare earth elements and essentially contains La, an A element which is Ba and / or Sr, Fe and Co as essential elements, Ca, R,
- the composition ratio of metal elements of A, Fe and Co is General formula Ca 1-xy R x A y Fe 2 n -z Co z (However, 1-xy, x, y, z representing atomic ratio of Ca, R element, A element and Co, and n representing molar ratio, respectively, 0.3 ⁇ 1-xy ⁇ 0.65, 0.2 ⁇ x ⁇ 0.65,
- the ferrite phase has a hexagonal M-type magnetoplumbite structure represented by 0 ⁇ y ⁇ 0.2, 0.03 ⁇ z ⁇ 0.65, and 4 ⁇ n ⁇ 7.
- the number of moles of oxygen varies depending on the valence of Fe and Co, n value, the type of R element, and the like.
- the ratio of oxygen to metal elements changes due to oxygen vacancies (vacancy) when fired in a reducing atmosphere, changes in the valence of Fe in the ferrite phase, changes in the valence of Co, etc. Do. Therefore, the actual number of moles of oxygen ⁇ may deviate from nineteen. Therefore, in the present invention, the composition is indicated by the metal element whose composition is most easily identified.
- a calcined ferrite body is a powder of oxide, a compound which becomes an oxide by calcination (a Ca compound, a compound of R element, and optionally a Ba compound and / or a Sr compound) Powders, iron compounds and powders of Co compounds) are mixed to obtain the above composition, and the resulting mixture is calcined (ferritized).
- a Ca compound, a compound of R element, and optionally a Ba compound and / or a Sr compound Powders, iron compounds and powders of Co compounds
- oxides, carbonates, hydroxides, nitrates, chlorides and the like of the respective metals can be used regardless of the valence number. It may be a solution in which the raw material powder is dissolved.
- a Ca compound carbonates, oxides, chlorides and the like of Ca are used.
- oxides such as La 2 O 3 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 are used.
- oxides, hydroxides, carbonates and the like of mixed rare earths (La, Nd, Pr, Ce etc.) are preferable because they are inexpensive and cost can be reduced.
- As a compound of the element A carbonates, oxides, chlorides and the like of Ba and / or Sr are used.
- As the iron compound iron oxide, iron hydroxide, iron chloride, mill scale or the like is used.
- As the Co compound oxides such as CoO and Co 3 O 4 , hydroxides such as CoOOH, Co (OH) 2 , 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 Do.
- Raw material powders other than CaCO 3 , Fe 2 O 3 and La 2 O 3 may be added from the time of mixing the raw materials, or may be added after calcination.
- CaCO 3 , Fe 2 O 3 , La 2 O 3 and Co 3 O 4 are blended, mixed and calcined, and then the calcined body is crushed, shaped and sintered to obtain a ferrite sintered magnet
- CaCO 3 , Fe 2 O 3 and La 2 O 3 are blended, mixed and calcined, and then Co 3 O 4 is added to the calcined body, pulverized, shaped and It is also possible to produce a ferrite sintered magnet by sintering.
- a compound containing B such as B 2 O 3 or H 3 BO 3 may be added at about 1% by mass or less, if necessary.
- H 3 BO 3 is effective in further improvement of H cJ and B r.
- the amount of H 3 BO 3 added is preferably 0.3% by mass or less, and most preferably about 0.2% by mass. Amount of H 3 BO 3 is less effect of improving low and B r than 0.1 wt%, B r is reduced as more than 0.3 mass%.
- H 3 BO 3 also has the effect of controlling the shape and size of crystal grains at the time of sintering, and therefore may be added after calcination (before pulverization or before sintering), before calcination and after calcination It may be added by both.
- Blending of the raw material powder may be carried out either wet or dry. Stirring with a medium such as steel balls allows the raw material powders to be mixed more uniformly. When wet, it is preferable to use water as the solvent. In order to improve the dispersibility of the raw material powder, known dispersants such as ammonium polycarboxylate and calcium gluconate may be used. The mixed raw material slurry is dehydrated to obtain a mixed raw material powder.
- the mixed raw material powder undergoes solid phase reaction by heating using an electric furnace, a gas furnace or the like to form a ferrite compound having a hexagonal M-type magnetoplumbite structure. This process is called “calcination” and the obtained compound is called “calcination”.
- the calcination step is preferably performed in an atmosphere having an oxygen concentration of 5% or more. If the oxygen concentration is less than 5%, abnormal grain growth, formation of a heterophase and the like are caused. A more preferable oxygen concentration is 20% or more.
- the solid phase reaction in which the ferrite phase is formed proceeds with the increase of temperature and is completed at about 1100 ° C. If the calcination temperature is less than 1100 ° C., unreacted hematite (iron oxide) remains, and the magnetic properties become poor. On the other hand, when the calcining temperature exceeds 1450 ° C., crystal grains grow too much, so it may take a long time to grind in the grinding step. Therefore, the calcination temperature is preferably 1100 to 1450 ° C., and more preferably 1200 to 1350 ° C. The calcination time is preferably 0.5 to 5 hours.
- SiO 2 is most preferably added to the calcined body, it may be added to a portion of the total amount pre-calcination (when formulating a raw material powder). By adding before calcination, it is possible to control the size of crystal grains at the time of calcination.
- a preferable addition amount of SiO 2 is slightly changed by the addition amount of the CaCO 3 (CaO conversion). In addition, as shown in the examples described later, it slightly changes depending on the content (z) of Co. For example, in view of the improvement effect of H cJ , regardless of the content (z) of Co, when the addition amount of CaCO 3 increases, the preferable addition amount of SiO 2 also tends to shift to the larger one. In addition, when the content of Co decreases, the preferred addition amount of SiO 2 tends to shift to the larger side. However, the addition amount of SiO 2 is too high B r and H k / H cJ is reduced.
- the addition amount of SiO 2 is 1.1 to 1.5 mass% and CaCO 3 addition amount (in terms of CaO) is preferably 1.2 to 2 mass%, and when Co content (z) is z ⁇ 0.3, the addition amount of SiO 2 is 1.4 to 1.6 mass% and the addition amount of CaCO 3 (CaO 3 Is preferably 1.5 to 2% by mass, and in consideration of both, as described above, the addition amount of SiO 2 is preferably 1.1 to 1.6% by mass, and at this time, the addition amount of CaCO 3 (in terms of CaO) is 1.2 to 2 It is preferable that it is mass%.
- both SiO 2 and CaCO 3 when both SiO 2 and CaCO 3 are added, they may be suitably added within the range of the addition amount of SiO 2 and the addition amount of the CaCO 3 , preferably, as described above, SiO 2 by 2 amount of 1.1 in the range of ⁇ 1.6% by weight and CaCO 3 added amount (CaO equivalent) is set within the range of 1.2 to 2 mass%, high while maintaining a high B r and H k / H cJ A ferrite sintered magnet having H cJ is obtained.
- the magnetic properties can be further improved by setting [CaCO 3 addition amount (CaO equivalent) / SiO 2 addition amount] to 0.8 to 2.
- the preferable range of [CaCO 3 added amount (CaO converted) / SiO 2 added amount] slightly changes depending on the content (z) of Co as shown in the examples described later. In the case of z ⁇ 0.3, 1 to 1.7 is preferable, and 1.1 to 1.4 is more preferable. In the case of z ⁇ 0.3, 0.8 to 1.4 is preferable, and 0.9 to 1.1 is more preferable.
- the calcined body is pulverized by a vibration mill, a ball mill, an attritor or the like to obtain a pulverized powder.
- the average particle size of the pulverized powder is preferably about 0.4 to 0.8 ⁇ m (air permeation method).
- the grinding process may be either dry grinding or wet grinding, but it is preferable to carry out both in combination.
- wet grinding is performed using water and / or non-aqueous solvents (organic solvents such as acetone, ethanol, xylene, etc.). Wet grinding produces a slurry in which water (solvent) and a calcined body are mixed. It is preferable to add 0.2 to 2% by mass of a known dispersant and / or surfactant in solid content ratio to the slurry. After wet grinding, it is preferable to concentrate and knead the slurry.
- organic solvents such as acetone, ethanol, xylene, etc.
- Cr 2 O 3 , Al 2 O 3 or the like can be added in addition to the above-described SiO 2 and CaCO 3 in order to improve the magnetic properties.
- the addition amount of each of these is preferably 5% by mass or less.
- the pulverized powder contains ultrafine powder of less than 0.1 ⁇ m which causes dewatering deterioration and molding defects, it is preferable to heat treat the pulverized powder in order to remove these ultrafine powder.
- the heat-treated powder is preferably pulverized again.
- the step of subjecting the powder obtained in the first pulverizing step to heat treatment, and the second pulverizing step in which the heat-treated powder is again pulverized by adopting comprising milling step (hereinafter referred to as "heat treatment re-pulverizing step")
- heat treatment re-pulverizing step it is possible to further H cJ addition to H cJ improvement by the addition of SiO 2 and CaCO 3, it can not be obtained so far it is possible to provide a ferrite sintered magnet having maintaining high B r and H k / H cJ and much higher H cJ.
- ultrafine powder of less than 0.1 ⁇ m is unavoidably produced, and the presence of the ultrafine powder lowers H cJ , dewatering property deteriorates in the molding process, causes defects in the molded body, and dewatering. It takes a long time to reduce the press cycle.
- the powder containing the ultrafine powder obtained by the first pulverizing step is subjected to heat treatment, a reaction occurs between the relatively large particle size powder and the ultrafine powder, and the amount of ultrafine powder can be reduced.
- particle size adjustment and necking removal are performed by the second pulverizing step to prepare a powder of a predetermined particle size.
- the particle size of the powder in the second pulverizing step is set relatively large (for example, the average particle size is about 0.8 to 1.0 ⁇ m), it can be obtained by the usual pulverizing step by utilizing the improvement effect of H cJ in the heat treatment regrinding step.
- the same HcJ as in the case of using the powder (average particle size about 0.4 to 0.8 .mu.m) is obtained. Therefore, while being able to aim at time shortening by a 2nd pulverization process, the improvement of the further dewatering property and the press cycle can be aimed at.
- the heat treatment regrinding process although various advantages are obtained, as described above, the cost increase associated with the increase of the manufacturing process can not be avoided.
- the improvement effect of the magnetic properties obtained when the heat treatment re-pulverizing step is adopted is very large as compared to the case of manufacturing the conventional ferrite sintered magnet. You can offset the up. Therefore, in the present invention, the heat treatment regrinding step is a practically meaningful step.
- the first pulverization is the same as the above-mentioned usual pulverization, and is performed using a vibration mill, jet mill, ball mill, attritor or the like.
- the average particle size of the pulverized powder is preferably about 0.4 to 0.8 ⁇ m (air permeation method).
- the grinding process may be either dry grinding or wet grinding, but it is preferable to carry out both in combination.
- the heat treatment carried out after the first milling step is preferably performed at 600 to 1200 ° C., more preferably 800 to 1100 ° C.
- the heat treatment time is not particularly limited, but is preferably 1 second to 100 hours, and more preferably about 1 to 10 hours.
- the second pulverization to be performed after the heat treatment step is performed using a vibration mill, a jet mill, a ball mill, an attritor, or the like.
- a vibration mill a jet mill
- a ball mill a ball mill
- an attritor or the like.
- Most desired particle sizes are already obtained in the first milling step, so in the second milling step mainly particle size control and necking removal are carried out. Therefore, it is preferable to reduce the pulverizing conditions by shortening the pulverizing time or the like rather than the first pulverizing step. Crushing under the same conditions as in the first pulverizing step is not preferable because ultrafine powder is generated again.
- the average particle size of the powder after the second pulverization is about 0.4 to 0.8 ⁇ m (air permeation) as in the usual pulverization process when it is desired to obtain H cJ higher than the ferrite sintered magnet obtained by the usual pulverization process If you want to take advantage of advantages such as shortening the grinding process time, further improvement of the dewaterability, and improvement of the press cycle, it should be about 0.8 to 1.2 ⁇ m, preferably about 0.8 to 1.0 ⁇ m (air permeation method) It is preferable to
- the slurry after crushing is press-formed in a magnetic field or in a non-magnetic field while removing water (solvent).
- a magnetic field By pressing in a magnetic field, the crystal orientations of the powder particles can be aligned (orientated), and the magnet characteristics can be dramatically improved.
- 0.01 to 1% by mass of a dispersant or a lubricant may be added.
- the slurry may be concentrated as needed before molding. The concentration is preferably performed by centrifugation, a filter press or the like.
- Firing process The molded object obtained by press molding is baked after degreasing as needed. Firing is performed using an electric furnace, a gas furnace or the like.
- the 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, formation of a heterophase and the like are caused, and the magnet characteristics are degraded.
- 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 step is about 0.5 to 2 ⁇ m.
- a ferrite sintered magnet is finally produced through a known manufacturing process such as a processing step, a cleaning step, and an inspection step.
- the raw material powder was mixed in a wet ball mill for 4 hours, dried and sized.
- the resultant was calcined at 1300 ° C. for 3 hours in the atmosphere, and the obtained calcined body was roughly crushed by a hammer mill to obtain a roughly crushed powder.
- the amount of SiO 2 powder and CaCO 3 powder (CaO equivalent) shown in Table 1 is added to the roughly pulverized powder, and the wet ball mill using water as a solvent until the average particle size by air permeation method becomes 0.55 ⁇ m Finely ground.
- the resulting pulverized slurry was shaped at a pressure of about 50 MPa while applying a magnetic field of about 1.3 T so that the pressing direction and the magnetic field direction were parallel while removing the solvent.
- the obtained compact was fired at 1200 ° C. for 1 hour in the air to obtain a sintered magnet.
- H k is the second of J (magnitude of magnetization) -H (intensity of magnetic field) curve of the obtained sintered magnet In the quadrant, the value of H at a position where J becomes a value of 0.95 B r was measured.
- the measurement results are shown in FIGS. 1 to 3.
- the abscissa represents the addition amount of SiO 2 (mass%)
- the ordinate represents the residual magnetic flux density B r (T) (FIG. 1)
- the coercive force H cJ (FIG.
- FIG. 4 is a comparison of Sample 113 and Sample 119, and a sample with an addition amount of SiO 2 of 1% by mass or less from FIG. Sample 113 (1.2% by mass of SiO 2 and 1.5% by mass of CaO) and Sample 119 (SiO 2 in proportion to those in which the addition amount of SiO 2 is 1 mass% or less, which was conventionally considered to be the optimum addition amount.
- HcJ is improved by about 20% or more for 1.5% by mass and 2.0% by mass of CaO).
- the added amount of SiO 2 is 1 mass% or less of the sample H cJ (400 kA / m or less), the anisotropy field H but not greater than about 19% of the value of a, H cJ of the sample 113 and sample 119 becomes about 23% of the value of the anisotropic magnetic field H a, the material originally It can be seen that it is approaching the potential of Furthermore, the CaO / SiO 2 of the sample 113 and the sample 119 is 1.25 and 1.33, respectively, and considering the sample 109 having relatively excellent magnetic properties, the ratio of CaO / SiO 2 is in the range of about 1.1 to 1.4, It can be seen that excellent magnet characteristics can be obtained.
- the coercivity H cJ improves as the amount of CaO added increases, and the highest coercivity H cJ is obtained particularly when the amount of CaO added is 1.5% by mass and 2% by mass. Further, when CaO addition amount is in the range of 1.2 to 2 mass%, the coercivity H cJ became approximately 20% or more relative to the value of the anisotropy field H A of the CaLaCo ferrite was 0.3 atomic ratio of Co, If the CaO addition amount is in the range of 1.5 to 2 mass%, the coercivity H cJ became about 23% relative to the value of the anisotropic magnetic field H a.
- Formulated values of SiO 2 and CaO of sintered magnets of the sample 113 and the sample 114 and quantitative values by ICP (Inductively Coupled Plasma) emission spectral analysis are shown in Table 2.
- the formulation values are% by weight of added SiO 2 and CaO with respect to the sum of the total composition.
- SiO 2 added to the calcined body is contained as it is also in the sintered magnet.
- the reason why the quantitative value of SiO 2 is larger than the prescribed value is presumed to be because elements other than SiO 2 are analyzed relatively less than the prescribed value.
- the residual magnetic flux density B r , coercivity H cJ and squareness ratio H k / H cJ of the obtained sintered magnet were measured.
- the measurement results are shown in FIG. 6 to FIG. 6 to 8, the horizontal axis represents the addition amount of SiO 2 (mass%), the vertical axis represents the residual magnetic flux density B r (T) (FIG. 6), and the coercivity H cJ (FIG. 7).
- Each value is plotted as the squareness ratio H k / H cJ (FIG. 8), and the data of the same CaO addition amount are connected by a straight line.
- the amount of SiO 2 added is more than 1% by mass and the amount of CaO added is 1% by mass or more as in Example 1.
- high magnetic properties can be obtained, and superior magnetic properties can be obtained when the addition amount of SiO 2 is 1.4 to 1.6% by mass and the addition amount of CaO is 1.5 to 2% by mass.
- SiO 2 is 1.6% by weight and CaO is 1.5 mass%), while suppressing a decrease in B r and H k / H cJ minimized, H cJ was specifically improved.
- FIG. 9 shows a sample 215 (1.6% by mass of SiO 2 and 1.5% by mass of CaO) extracted from FIG. 7 and a sample with an addition amount of SiO 2 of 1% by mass or less.
- the sample 215 (1.6% by mass of SiO 2 and 1.5% by mass of CaO) is compared with the sample in which the addition amount of SiO 2 conventionally considered optimum is 1% by mass or less.
- the value of the anisotropy field H A of the CaLaCo ferrite was 0.2 Co atomic ratio results measured by SPD method, was 1.9 MA / m (about 23.9 kOe). Therefore, the amount of SiO 2 is 1 mass% or less of the sample H cJ (300 kA / m or less), the anisotropy field H but not greater than about 16% of the value of A, the sample 215 (SiO 2 It can be seen that 1.6% by mass, 1.5% by mass of CaO) is about 20% of the value of the anisotropic magnetic field HA , and it approaches the potential inherent to the material. Further, CaO / SiO 2 in the sample 215 is 0.94, in the range of CaO / SiO 2 ratio is about 0.9 and 1.1, it can be seen that excellent magnetic characteristics can be obtained.
- the residual magnetic flux density B r , coercivity H cJ and squareness ratio H k / H cJ of the obtained sintered magnet were measured.
- the measurement results are shown in FIG. 10 to FIG.
- the abscissa represents the amount of added SiO 2 (mass%)
- the ordinate represents the residual magnetic flux density B r (T) (FIG. 10)
- the coercive force H cJ (FIG. 11).
- the values are plotted with squareness ratio H k / H cJ (FIG. 12).
- Example 12 the samples 111 to 115 in Example 1 and the samples 211 to 217 in Example 2 are plotted together so that the tendency due to the content (z) of Co can be compared.
- the data of the content (z) of the same Co were connected by a straight line.
- FIG. 13 is a graph in which data of the same Co content (z) are connected by straight lines, with CaO / SiO 2 on the horizontal axis and the coercive force H cJ on the vertical axis, using these data.
- the magnet characteristics can be improved by setting CaO / SiO 2 to 0.8 to 2.0.
- the value of CaO / SiO 2 to achieve a high H cJ while maintaining high B r and H k / H cJ in the case of z 0.3, preferably 1 to 1.7, and more preferably 1.2-1.4,
- FIG. 11 indicates that the maximum value of H cJ tends to decrease with the decrease in the content (z) of Co.
- H cJ is improved 20% or more
- the value of H cJ to the value of the anisotropy field H a is the fact that improved 4% or more, it is certainly approaching the material inherent potential. Therefore, when providing the same HcJ magnet as a conventional CaLaCo ferrite sintered magnet, the content of rare and expensive Co and La can be reduced.
- Example 2 even in the composition of the content z of 0.2 of Co where high H cJ can not be expected so far and it is difficult to put into practical use, it becomes possible to obtain H cj at a practical level.
- a high-performance ferrite sintered magnet with reduced La can be provided at low cost.
- CaCO 3 powder, La (OH) 3 powder, SrCO 3 powder, BaCO 3 powder, Fe 2 O 3 powder and Co 3 O 4 powder, and SiO 2 powder and CaCO 3 powder to the total of these compounded powders A sintered magnet was produced in the same manner as in Example 1 except that the addition amount (in terms of CaO) was changed as shown in Table 5.
- the Sr atomic ratio (y1) and the Ba atomic ratio (y2) are also shown in Table 5.
- Samples 111 to 115 are sintered magnets evaluated in Example 1.
- H k is the second of J (magnitude of magnetization) -H (intensity of magnetic field) curve of the obtained sintered magnet In the quadrant, the value of H at a position where J becomes a value of 0.95 B r was measured.
- the measurement results are shown in FIG. 14 to FIG. In FIG. 14 to FIG. 16, the abscissa represents the SiO 2 addition amount (mass%), and the ordinate represents the residual magnetic flux density B r (T) (FIG. 14), the coercive force H cJ (FIG.
- FIG. 17 is a graph in which the abscissa represents CaO / SiO 2 and the ordinate represents the coercive force H cJ from these data.
- the abscissa represents CaO / SiO 2
- the ordinate represents the coercive force H cJ from these data.
- the residual magnetic flux density B r , coercivity H cJ and squareness ratio H k / H cJ of the obtained sintered magnet were measured. The measurement results are shown in FIGS. 18 to 20.
- the finely divided slurry obtained by the above heat treatment regrinding step was formed under a pressure of about 50 MPa while applying a magnetic field of about 1.3 T so that the pressure direction and the magnetic field direction were parallel while removing the solvent. .
- the obtained compact was fired at 1200 ° C. for 1 hour in the air to obtain a sintered magnet.
- a sintered magnet was obtained in the same manner as described above, except that the heat treatment and the second pulverization were not performed, and the average particle size was changed to 0.8 ⁇ m (air permeation method) only by the first pulverization.
- H cJ 476 kA / m
- Br 0.443 T
- H k / H cJ 81.6%.
Abstract
Description
Ca、希土類元素の少なくとも1種であってLaを必須に含むR元素、Ba及び/又はSrであるA元素、Fe及びCoを必須元素とし、Ca、R、A、Fe及びCoの金属元素の組成比が、
一般式 Ca1-x-yRxAyFe2n-zCoz
により表わされ、
それぞれCa、R元素、A元素及びCoの原子比率を表わす1-x-y、x、y、z、及びモル比を表わすnが、
0.3≦1-x-y≦0.65、
0.2≦x≦0.65、
0≦y≦0.2、
0.03≦z≦0.65、及び
4≦n≦7
を満たす六方晶のM型マグネトプランバイト構造を有するフェライト相を含有するフェライト仮焼体を準備する工程、
前記仮焼体を粉砕し、粉末を得る粉砕工程、
前記粉末を成形し、成形体を得る成形工程、
前記成形体を焼成し、焼結体を得る焼成工程を含み、
前記粉砕工程の前に、前記仮焼体に、仮焼体100質量%に対して1質量%を超え、1.8質量%以下のSiO2を添加することを特徴とする。
0.35≦1-x-y≦0.55、
0.4≦x≦0.6、
0≦y≦0.15、
0.1≦z≦0.4、及び
4.5≦n≦6
であるのが好ましい。
0.42≦1-x-y≦0.5、
0.45≦x≦0.55、
0≦y≦0.08、
0.2≦z≦0.3、及び
4.8≦n≦5.2
であるのが好ましい。
一般式 Ca1-x-yRxAyFe2n-zCoz
により表わされ、
それぞれCa、R元素、A元素及びCoの原子比率を表わす1-x-y、x、y、z、及びモル比を表わすnが、
0.3≦1-x-y≦0.65、
0.2≦x≦0.65、
0≦y≦0.2、
0.03≦z≦0.65、及び
4≦n≦7
を満たす六方晶のM型マグネトプランバイト構造を有するフェライト相と、Siを必須に含む粒界相とを有するフェライト焼結磁石であって、
前記Siの含有量が、フェライト焼結磁石全体に対してSiO2換算で1質量%を超え、1.8質量%以下であることを特徴とする。
0.35≦1-x-y≦0.55、
0.4≦x≦0.6、
0≦y≦0.15、
0.1≦z≦0.4、及び
4.5≦n≦6
であるのが好ましい。
0.42≦1-x-y≦0.5、
0.45≦x≦0.55、
0≦y≦0.08、
0.2≦z≦0.3、及び
4.8≦n≦5.2
であるのが好ましい。
本発明のフェライト焼結磁石は、Ca、希土類元素の少なくとも1種であってLaを必須に含むR元素、Ba及び/又はSrであるA元素、Fe及びCoを必須元素とし、Ca、R、A、Fe及びCoの金属元素の組成比が、
一般式 Ca1-x-yRxAyFe2n-zCozにより表わされ、
それぞれCa、R元素、A元素及びCoの原子比率を表わす1-x-y、x、y、z、及びモル比を表わすnが、
0.3≦1-x-y≦0.65、
0.2≦x≦0.65、
0≦y≦0.2、
0.03≦z≦0.65、及び
4≦n≦7
を満たす六方晶のM型マグネトプランバイト構造を有するフェライト相と、Siを必須に含む粒界相とを有するフェライト焼結磁石であって、
前記Siの含有量が、フェライト焼結磁石全体に対してSiO2換算で1質量%を超え、1.8質量%以下であることを特徴とする。
フェライト焼結磁石は、フェライト仮焼体を準備する工程、前記仮焼体を粉砕し、粉末を得る粉砕工程、前記粉末を成形し成形体を得る成形工程、前記成形体を焼成し焼結体を得る焼成工程により製造する。ここで前記粉砕工程の前に、前記仮焼体に、仮焼体100質量%に対して1質量%を超え、1.8質量%以下のSiO2を添加することにより、焼結磁石の保磁力HcJを著しく向上させることができる。
一般式 Ca1-x-yRxAyFe2n-zCoz
(但し、それぞれCa、R元素、A元素及びCoの原子比率を表わす1-x-y、x、y、z、及びモル比を表わすnが、0.3≦1-x-y≦0.65、0.2≦x≦0.65、0≦y≦0.2、0.03≦z≦0.65、及び4≦n≦7を満たす。)により表わされる六方晶のM型マグネトプランバイト構造を有するフェライト相を有している。
一般式 Ca1-x-yRxAyFe2n-zCozOα
(但し、1-x-y、x、y、z、αはそれぞれCa、R元素、A元素、Co及びOの原子比率を表わし、nはモル比を表わし、0.3≦1-x-y≦0.65、0.2≦x≦0.65、0≦y≦0.2、0.03≦z≦0.65、及び4≦n≦7を満たし、R元素とFeが3価でCoが2価であり、x=zでかつn=6の時の化学量論組成比を示した場合はα=19である)で表される。
フェライト仮焼体は、酸化物の粉末、仮焼により酸化物となる化合物(Ca化合物、R元素の化合物、必要に応じてBa化合物及び/又はSr化合物の粉末、鉄化合物、Co化合物の粉末)を上記の組成になるように配合し、得られた混合物を仮焼(フェライト化)することにより製造する。なお、Ca、R元素、A元素、Fe及びCoの各元素の組成の限定理由は、上述したフェライト焼結磁石の場合と同様である。
本発明の製造方法は、粉砕工程の前に、仮焼体100質量%に対して1質量%を超え、1.8質量%以下のSiO2を仮焼体に添加するのが特徴である。これによって、HcJが特異的に向上する。SiO2の添加量が1質量%以下ではHcJの向上効果が得られず、1.8質量%を超えるとHcJが低下するとともに、Br及びHk/HcJも低下するため好ましくない。より好ましい添加量は1.1~1.6質量%である。
SiO2の添加量に応じて、粉砕工程の前に、仮焼体100質量%に対してCaCO3をCaO換算で1~2質量%添加するのが好ましい。CaCO3の添加によって、BrやHk/HcJの低下が極力防止でき、従来は得ることができなかった高いBr及びHk/HcJを維持しつつ、高いHcJを有するフェライト焼結磁石が得られる。CaCO3の添加量(CaO換算)が1質量%未満及び2質量%を超えるとBr及びHk/HcJが低下するため好ましくない。より好ましい添加量は1.2~2質量%である。
仮焼体は、振動ミル、ボールミル、アトライター等によって粉砕し、粉砕粉とする。粉砕粉の平均粒度は0.4~0.8μm程度(空気透過法)にするのが好ましい。粉砕工程は、乾式粉砕及び湿式粉砕のいずれもよいが、双方を組み合わせて行うのが好ましい。
粉砕後のスラリーは、水(溶剤)を除去しながら磁界中又は無磁界中でプレス成形する。磁界中でプレス成形することにより、粉末粒子の結晶方位を整列(配向)させることができ、磁石特性を飛躍的に向上させることができる。さらに、配向を向上させるために、分散剤、潤滑剤を0.01~1質量%添加しても良い。また成形前にスラリーを必要に応じて濃縮してもよい。濃縮は遠心分離、フィルタープレス等により行うのが好ましい。
プレス成形により得られた成形体は、必要に応じて脱脂した後、焼成する。焼成は、電気炉、ガス炉等を用いて行う。
組成式Ca1-x-yLaxAyFe2n-zCozO19-δにおいて、x=0.5、y=0、z=0.3、n=5.2及びδ≧0になるように配合したCaCO3粉末、La(OH)3粉末、Fe2O3粉末及びCo3O4粉末に、前記配合後の粉末の合計100質量%に対してH3BO3粉末を0.1質量%添加し原料粉末を得た。この原料粉末を湿式ボールミルで4時間混合し、乾燥して整粒した。大気中において1300℃で3時間仮焼し、得られた仮焼体をハンマーミルで粗粉砕して粗粉砕粉を得た。
組成式Ca1-x-yLaxAyFe2n-zCozO19-δにおいて、x=0.5、y=0、z=0.2、n=4.8及びδ≧0とし、SiO2粉末とCaCO3粉末(CaO換算)とを表3に示す量添加した以外は実施例1と同様にして焼結磁石を作製した。
組成式Ca1-x-yLaxAyFe2n-zCozO19-δにおいて、x=0.5、y=0、z=0.25、n=5.0及びδ≧0とし、SiO2粉末とCaCO3粉末(CaO換算)とを表4に示す量添加した以外は実施例1と同様にして焼結磁石を作製した。
組成式Ca1-x-y1-y2LaxSry1Bay2Fe2n-zCozO19-δにおいて、x=0.5、y1+y2=0.05、z=0.3、n=5.3及びδ≧0となるように、CaCO3粉末、La(OH)3粉末、SrCO3粉末、BaCO3粉末、Fe2O3粉末及びCo3O4粉末を配合し、これらの配合粉末の合計に対するSiO2粉末及びCaCO3粉末(CaO換算)の添加量を表5に示すように変更した以外は実施例1と同様にして焼結磁石を作製した。Sr原子比(y1)及びBa原子比(y2)も合わせて表5に示す。試料111~115は実施例1で評価した焼結磁石である。
組成式Sr1-xLaxFe2n-zCozO19-δにおいて、x=0.2、z=0.2、n=5.8及びδ≧0となるように、SrCO3粉末、La(OH)3粉末、Fe2O3粉末及びCo3O4粉末を配合し、SiO2粉末及びCaCO3粉末(CaO換算)の添加量を表6に示すように変更した以外は実施例1と同様にして焼結磁石を作製した。これらの焼結磁石は、基本組成が本願発明から外れる、いわゆるSrLaCoフェライト磁石である。
組成式Ca1-x-yLaxAyFe2n-zCozO19-δにおいて、x=0.5、y=0、z=0.3、n=5.2及びδ≧0になるように配合したCaCO3粉末、La(OH)3粉末、Fe2O3粉末及びCo3O4粉末に、前記配合後の粉末100質量%に対してH3BO3粉末を0.1質量%添加し原料粉末を得た。この原料粉末を湿式ボールミルで4時間混合し、乾燥して整粒した。大気中において1300℃で3時間仮焼し、得られた仮焼体をハンマーミルで粗粉砕して粗粉砕粉を得た。
Claims (11)
- 六方晶のM型マグネトプランバイト構造を有するフェライト相と、Siを必須に含む粒界相とを有するフェライト焼結磁石の製造方法であって、
Ca、希土類元素の少なくとも1種であってLaを必須に含むR元素、Ba及び/又はSrであるA元素、Fe及びCoを必須元素とし、Ca、R、A、Fe及びCoの金属元素の組成比が、
一般式 Ca1-x-yRxAyFe2n-zCoz
により表わされ、
それぞれCa、R元素、A元素及びCoの原子比率を表わす1-x-y、x、y、z、及びモル比を表わすnが、
0.3≦1-x-y≦0.65、
0.2≦x≦0.65、
0≦y≦0.2、
0.03≦z≦0.65、及び
4≦n≦7
を満たす六方晶のM型マグネトプランバイト構造を有するフェライト相を含有するフェライト仮焼体を準備する工程、
前記仮焼体を粉砕し、粉末を得る粉砕工程、
前記粉末を成形し、成形体を得る成形工程、
前記成形体を焼成し、焼結体を得る焼成工程を含み、
前記粉砕工程の前に、前記仮焼体に、仮焼体100質量%に対して1質量%を超え、1.8質量%以下のSiO2を添加することを特徴とするフェライト焼結磁石の製造方法。 - 請求項1に記載のフェライト焼結磁石の製造方法において、粉砕工程前に、仮焼体に、仮焼体100質量%に対してCaO換算で1~2質量%のCaCO3を添加することを特徴とするフェライト焼結磁石の製造方法。
- 請求項1又は2に記載のフェライト焼結磁石の製造方法において、SiO2の添加量が1.1~1.6質量%であることを特徴とするフェライト焼結磁石の製造方法。
- 請求項1~3のいずれかに記載のフェライト焼結磁石の製造方法において、CaOの添加量が1.2~2質量%であることを特徴とするフェライト焼結磁石の製造方法。
- 請求項1~4のいずれかに記載のフェライト焼結磁石の製造方法において、1-x-y、x、y、z及びnが、
0.35≦1-x-y≦0.55、
0.4≦x≦0.6、
0≦y≦0.15、
0.1≦z≦0.4、及び
4.5≦n≦6
であることを特徴とするフェライト焼結磁石の製造方法。 - 請求項1~5のいずれかに記載のフェライト焼結磁石の製造方法において、1-x-y、x、y、z及びnが、
0.42≦1-x-y≦0.5、
0.45≦x≦0.55、
0≦y≦0.08、
0.2≦z≦0.3、及び
4.8≦n≦5.2
であることを特徴とするフェライト焼結磁石の製造方法。 - 請求項1~6のいずれかに記載のフェライト焼結磁石の製造方法において、前記粉砕工程が、第一の微粉砕工程と、前記第一の微粉砕工程によって得られた粉末に熱処理を施す工程と、前記熱処理が施された粉末を再度粉砕する第二の微粉砕工程とからなることを特徴とするフェライト焼結磁石の製造方法。
- Ca、希土類元素の少なくとも1種であってLaを必須に含むR元素、Ba及び/又はSrであるA元素、Fe及びCoを必須元素とし、Ca、R、A、Fe及びCoの金属元素の組成比が、
一般式 Ca1-x-yRxAyFe2n-zCoz
により表わされ、
それぞれCa、R元素、A元素及びCoの原子比率を表わす1-x-y、x、y、z、及びモル比を表わすnが、
0.3≦1-x-y≦0.65、
0.2≦x≦0.65、
0≦y≦0.2、
0.03≦z≦0.65、及び
4≦n≦7
を満たす六方晶のM型マグネトプランバイト構造を有するフェライト相と、Siを必須に含む粒界相とを有するフェライト焼結磁石であって、
前記Siの含有量が、フェライト焼結磁石全体に対してSiO2換算で1質量%を超え、1.8質量%以下であることを特徴とするフェライト焼結磁石。 - 請求項8に記載のフェライト焼結磁石において、Siの含有量が、フェライト焼結磁石全体に対してSiO2換算で1.1~1.6質量%であることを特徴とするフェライト焼結磁石。
- 請求項8又は9に記載のフェライト焼結磁石において、1-x-y、x、y、z及びnが、
0.35≦1-x-y≦0.55、
0.4≦x≦0.6、
0≦y≦0.15、
0.1≦z≦0.4、及び
4.5≦n≦6
であることを特徴とするフェライト焼結磁石。 - 請求項8~10のいずれかに記載のフェライト焼結磁石において、1-x-y、x、y、z及びnが、
0.42≦1-x-y≦0.5、
0.45≦x≦0.55、
0≦y≦0.08、
0.2≦z≦0.3、及び
4.8≦n≦5.2
であることを特徴とするフェライト焼結磁石。
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EP2450922A4 (en) | 2013-11-27 |
US9162928B2 (en) | 2015-10-20 |
US20120105185A1 (en) | 2012-05-03 |
KR101649242B1 (ko) | 2016-08-18 |
SI2450922T1 (sl) | 2018-11-30 |
EP2450922B1 (en) | 2018-07-25 |
US9773593B2 (en) | 2017-09-26 |
US20150332819A1 (en) | 2015-11-19 |
CN102473514B (zh) | 2014-04-09 |
KR20120047245A (ko) | 2012-05-11 |
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EP2450922A1 (en) | 2012-05-09 |
HUE040207T2 (hu) | 2019-03-28 |
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