CN103848622A - Ferrite compound - Google Patents

Ferrite compound Download PDF

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CN103848622A
CN103848622A CN201310195158.4A CN201310195158A CN103848622A CN 103848622 A CN103848622 A CN 103848622A CN 201310195158 A CN201310195158 A CN 201310195158A CN 103848622 A CN103848622 A CN 103848622A
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ferrite
sintered magnet
rate
burning
heat
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尾田悦志
小林义德
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Proterial Ltd
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Hitachi Metals Ltd
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Abstract

The invention relates to a ferrite compound having a hexagonal M-type magnetoplumbite structure and containing Ca, La, Fe and Co as essential components, wherein the total amount of Ca present in 2a, 4e, 4f1, 4f2 and 12k sites in a unit cell of the M-type magnetoplumbite structure is 0.05 particle/unit cell or more.

Description

Ferrite compounds
Technical field
The present invention relates to the ferrite compounds used such as ferrite sintered magnet.
Background technology
Ferrite sintered magnet, is used to all purposes such as various electric motor, generator, loud speaker.As representational ferrite sintered magnet, the known Sr ferrite (SrFe that has the M type magnetoplumbite type with hexagonal crystal 12o 19) and Ba ferrite (BaFe 12o 19).These ferrite sintered magnets, taking carbonate of ferric oxide and strontium (Sr) or barium (Ba) etc. as raw material, by powder metallurgic method less expensive manufacture.
In recent years, from for environmental consideration grade, with in part etc., taking small-sized, the lightweight of part and high efficiency as object, require the high performance of ferrite sintered magnet at automobile electrical dress part, electric installation.In the electric motor particularly using at automobile electrical dress part, require ferrite sintered magnet should keep high residue magneticflux-density B r(following, be only called " B r"), meanwhile, even also can demagnetize under the strong diamagnetism field action in the time of slimming, still there is high coercivity H cJ(following, be only called " H cJ") and high squareness ratio H k/ H cJ(following, be only called " H k/ H cJ").At this, H kthat J is for J in the second quadrant of J (magnetized size)-H (intensity in magnetic field) curve rthe value of (residual magnetization) reaches the value (same below) of the H of the position of the value of certain ratio.As the value of described certain ratio, use be 0.90J rto 0.95J r.
In order to realize the raising of magnet characteristic of ferrite sintered magnet, by replace a part of the Sr in above-mentioned Sr ferrite with the rare earth element of La etc., with a part for Co replacement of fe, thereby make H cJand B rthe method improving, is proposed for No. 11-154604 by No. 10-149910, Unexamined Patent and Unexamined Patent.
Described in No. 11-154604, No. 10-149910, Unexamined Patent and Unexamined Patent, with a part of the rare earth element displacement Sr of La etc., with the Sr ferrite (hereinafter referred to as " SrLaCo ferrite ") of the parts of the replacement of fe such as Co, due to magnet excellent, be used for various uses so replacing existing Sr ferrite and Ba ferrite, but also expect the further raising of magnet characteristic.
No. 2001-223104, JP, in order to realize the ferritic H of described SrLaCo cJraising, propose in the temperature-rise period of firing process, making 900 DEG C of heat-up rates to the temperature range of top temperature is 1～5 DEG C/min.In the embodiment of No. 2001-223104, JP, describe, at Sr 1-xla x(Fe 12 -yco y) zo 19composition in, be 1～5 DEG C/min by making heat-up rate, H cJimprove.Further, JP is described for No. 2001-223104, and cooling rate is not particularly limited, and is generally 1～20 DEG C/min, and in embodiment, making cooling rate is 5 DEG C/min.
On the other hand, as ferrite sintered magnet, together with above-mentioned Sr ferrite and Ba ferrite, also known have a Ca ferrite.Known Ca ferrite is by CaO-Fe 2o 3or CaO-2Fe 2o 3the construction of stable that represents of composition formula, form hexagonal crystal ferrite by adding La.But the ferritic magnet characteristic of the magnet characteristic obtaining and existing Ba is same degree, fully do not improve.
No. 3181559th, patent, in order to realize the ferritic B of Ca rand H cJraising, and H cJthe improvement of temperature profile, disclose a part of a kind of rare earth element displacement Ca with La etc., with the parts of the replacement of fe such as Co, there is anisotropy field H more than 20kOe a(following, be only called " H a") Ca ferrite (hereinafter referred to as " CaLaCo ferrite "), and describe its H acompared with Sr ferrite, it is high more than 10% value.
But CaLaCo ferrite, although have the ferritic H of the SrLaCo of exceeding abut, B rand H cJwith SrLaCo ferrite be same degree, on the other hand, H k/ H cJnon-constant, can not meet high H cJwith high H k/ H cJ, cannot reach the level of the various uses that is applied to electric motor etc.
In order to improve the ferritic magnet characteristic of CaLaCo, all motions are proposed.For example, JP proposes for No. 2006-104050, make the value optimizing of atom ratio and the mol ratio n of each Constitution Elements, and the CaLaCo ferrite that contains La and Co with specific ratio, International Publication proposes for No. 2007/060757, replace the CaLaCo ferrite of a part of Ca with La and Ba, International Publication proposes for No. 2007/077811, replaces the CaLaCo ferrite of a part of Ca with La and Sr.
But, CaLaCo ferrite described in No. 2007/077811st, No. 2006-104050, JP, No. 2007/060757th, International Publication and International Publication, the CaLaCo ferrite proposing for No. 3181559 with respect to patent, although magnet characteristic all increases, but the requirement of the high performance that reply strengthens in recent years is day by day still insufficient, wishes the further raising of magnet characteristic.
International Publication proposes to have a kind of CaLaCo ferrite No. 2011/001831, it is in the CaLaCo ferrite proposing for No. 2007/077811 in No. 2006-104050, JP, No. 2007/060757th, International Publication and International Publication, as sintering aid, 1 quality %, SiO below 1.8 quality % will be exceeded 2, and be scaled the CaCO of 1～2 quality % with CaO 3add in pre-burning body, do one's utmost to prevent thus B on one side rand H k/ H cJreduction, make on one side H cJimprove clearly.
The CaLaCo ferrite that contains relatively large sintering aid that International Publication proposes for No. 2011/001831, although H cJimprove clearly, but it most, if H cJexceed 360kA/m (about 4.5kOe), H k/ H cJbe reduced to lower than 85%, cannot say for sure fully towards the reply of the slimming of desired ferrite sintered magnet in recent years.
Summary of the invention
Therefore, the object of the invention is to, provide a kind of in CaLaCo ferrite, maintaining high B rwith high H k/ H cJstate under make H cJimprove, can tackle slimming as the useful ferrite compounds of the formation compound of ferrite sintered magnet.
In view of above-mentioned purpose and the with keen determination result of research, inventors have found to have in the ferritic crystalline texture of CaLaCo, the ferrite compounds of the M type magnetoplumbite type that a part for the brilliant position that Fe or Co occupy is replaced by Ca.But also find, the ferrite sintered magnet using crystallization phases (ferrite phase) that this ferrite compounds was formed as principal phase, has high B rwith high H k/ H cJ, and there is high H cJthereby, completed the present invention.
, ferrite compounds of the present invention, is characterized in that, it is the M type magnetoplumbite type with hexagonal crystal, contain Ca, La, Fe and the Co ferrite compounds as essential component, wherein, be present in 2a, 4e, 4f in the unit cell of described M type magnetoplumbite type 1, 4f 2with in the total amount per unit structure cell of the Ca of the brilliant position of 12k, be more than 0.05.
Preferred described ferrite compounds, is representing Ca, La, composition formula as the atom ratio of the metallic element of A element, Fe and the Co of Ba and/or Sr: Ca 1-x-yla xa yfe 2n-z-wco zca win, the n of described 1-x-y, x, y, z, w and expression mol ratio, meets
0.23≤(1-x-y+w)/(1+w)≤0.75、
0.2≤x/(1+w)≤0.65、
0≤y/(1+w)≤0.4、
0.2≤z/(1+w)＜0.65、
w≥0.025
3 < n/ (1+w) < 6 Hes
0≤y/(1-x+w)＜0.56。
Described ferrite compounds, preferably manufacture in the following way: pulverize the pre-burning body that pre-burning raw material powder forms, taking the heat-up rate in the temperature range of 1100 DEG C～firing temperature as 1～4 DEG C/min, and cooling rate in the temperature range of firing temperature～1100 DEG C is that more than 6 DEG C/min condition is burnt till.
Ferrite compounds of the present invention has high saturation and high H a, therefore, by for sintered magnet, bonded permanent magnet, magnetic recording medium etc., can give play to high-performance.While particularly use as the main compound that forms ferrite sintered magnet, can obtain maintaining high B rwith high H k/ H cJstate under make H cJthe ferrite sintered magnet improving, can tackle slimming, by using this ferrite sintered magnet, can provide automobile electrical dress part, the electric installation part etc. of the various electric motor, generator, loud speaker etc. of small-sized, lightweight, high efficiency.
Brief description of the drawings
Fig. 1 is heat-up rate and the B in firing process of the ferrite sintered magnet of test portion No.1～8 that represents embodiment 1 r(bullet) and H cJthe figure of the relation of (black triangle).
Fig. 2 is heat-up rate and the H in firing process of the ferrite sintered magnet of test portion No.1～8 that represents embodiment 1 k/ H cJthe figure of relation.
Fig. 3 represents test portion No.9～13 (bullet) of embodiment 1 and cooling rate and the B of the ferrite sintered magnet of test portion No.14～18 (black triangle) in firing process rand H cJthe figure of relation.
Fig. 4 represents test portion No.9～13 (bullet) of embodiment 1 and cooling rate and the H of the ferrite sintered magnet of test portion No.14～18 (black triangle) in firing process k/ H cJthe figure of relation.
Fig. 5 is heat-up rate and the B in firing process of the ferrite sintered magnet of test portion No.19～26 that represents embodiment 1 r(bullet) and H cJthe figure of the relation of (black triangle).
Fig. 6 is heat-up rate and the H in firing process of the ferrite sintered magnet of test portion No.19～26 that represents embodiment 1 k/ H cJthe figure of relation.
Embodiment
[1] ferrite compounds
Ferrite compounds of the present invention, it is characterized in that, be the M type magnetoplumbite type with hexagonal crystal, contains Ca, La, Fe and the Co ferrite compounds as essential component, wherein, be present in 2a, 4e, 4f1, the 4f in the unit cell of described M type magnetoplumbite type 2with in the total amount per unit structure cell of the Ca of the brilliant position of 12k, be more than 0.05.
Ferrite compounds of the present invention has the M type magnetoplumbite type of hexagonal crystal.When so-called " having the M type magnetoplumbite type of hexagonal crystal " refers to the ferrite sintered magnet that contains the crystallization phases (ferrite phase) being made up of ferrite compounds of the present invention with the general conditioned measurement of X-ray diffraction method and ferrite powder, what mainly observe is the X-ray diffraction pattern of the M type magnetoplumbite type of hexagonal crystal.
The M type magnetoplumbite type of hexagonal crystal is complicated crystalline texture, in the ferritic situation of Sr, has the 2d that Sr occupies, 2a, 4e, 4f1,4f that Fe occupies 2and 12k, and O (oxygen) 4e, the 4f, 6h, the 12k that occupy 1and 12k 211 kinds of different brilliant positions.Formula unit number in per unit structure cell is 2, the atom that contains Chemical formula 2 part in per unit structure cell.For example, (chemical formula is SrFe to Sr ferrite 12o 19) situation under, in per unit structure cell, contain 2 Sr, 24 Fe and 38 O.
In aforesaid SrLaCo ferrite, known La exists in the part of the brilliant position of 2d (crystalline substance of Sr), and Co is at 2a, 4e, 4f1,4f 2exist with the part of the brilliant position of 12k (the brilliant position of Fe) (for example, with reference to J.Ceram.Soc.Jpn., 119 (2011) 285-290).In addition, in aforesaid CaLaCo ferrite, also same with SrLaCo ferrite, think that Ca, La exist in a part for the brilliant position of 2d respectively, Co is at 2a, 4e, 4f1,4f 2exist with a part for the brilliant position of 12k, the composition of existing ferrite sintered magnet designs under such idea.The composition formula that No. 2007/077811st, No. 2006-104050, the aforesaid JP of these content viewings, No. 2007/060757th, International Publication and International Publication etc. are described is known.
In CaLaCo ferrite, in existing Sr ferrite and Ba ferrite, at original Sr (with the Sr of 12 coordinations 2+ionic radius: 144pm) and Ba (with the Ba of 12 coordinations 2+ionic radius: 161pm) part of the brilliant position occupied, Ca is (with the Ca of 12 coordinations in displacement 2+ionic radius: 134pm, the ionic radius with 6 coordinations: 100pm) and La (with the La of 12 coordinations 3+ionic radius: 136pm), at Fe (with the Fe of 6 coordinations 3+ionic radius: 64.5pm) part of the brilliant position occupied, Co is (with the Co of 6 coordinations in displacement 2+ionic radius: 74.5pm), therefore with without displacement Sr ferrite compare with Ba ferrite, think that the crystalline texture of M type magnetoplumbite produces huge distortion.And in CaLaCo ferrite, the La ion of 3 valencys is for the replacement amount of the Ca ion of divalent, significantly different for the replacement amount of the Fe ion of 3 valencys from the Co ion of divalent, all charge balances of crystallization produce unbalanced, need to keep all charge balances of crystallization with certain methods.For this reason, the ferritic crystalline texture of CaLaCo does not have Sr ferrite and SrLaCo ferrite to stablize.
In ferrite compounds of the present invention, be present in 2a, 4e, 4f1,4f in the unit cell of M type magnetoplumbite type 2with in the total amount per unit structure cell of the Ca of the brilliant position of 12k, be more than 0.05.There is following structure: in per unit structure cell, have among the brilliant position of 24 Fe and Co existence, more than 0.05 replaced by Ca.A part by the brilliant position of Fe is replaced by Ca, and the unbalanced of the distortion of crystalline texture and charge balance relaxed, and thinks crystalline texture stabilization as M type magnetoplumbite type.
Be present in 2a, 4e, 4f1,4f in the unit cell of M type magnetoplumbite type 2with the total amount of the Ca of the brilliant position of 12k, the contour of the diffraction pattern that can be undertaken by X-ray diffraction and neutretto diffraction etc. is analyzed.X-ray diffraction for example can use the radiating light facility of SPring-8 etc. and the powder x-ray diffraction device of market sale to carry out, and neutron diffraction for example can be used the facility of JRR-3 of Japanese atomic power research and development organization etc. to carry out.
The contour that the analysis of the diffraction pattern carrying out as X-ray diffraction and neutron diffraction adopts, can enumerate for example Li Te Wald (Rietveld) analytical method.Li Te Wald is analyzed, to make the diffraction pattern that calculates according to the crystalline texture that is contemplated for material contained in test portion, with the diffraction pattern matching being obtained by X-ray diffraction etc., carry out the method for the analysis of accurate crystalline texture (coordinate of each brilliant position, kind and the occupation rate etc. of occupying the atom of each brilliant position).As Li Te Wald analysis software, can enumerate the software of the market sale of TOPAS (Bruker AXS society system) etc., and RIETAN-FP (F.Izumi and K.Momma, " Three-dimensional visualization in powder diffraction; " Solid State Phenom., 130,15-20 (2007) .) etc.The crystalline texture that forms phase is used known structure as original texture.
The present invention relates to the ferritic improvement of CaLaCo, ferrite compounds of the present invention, contains Ca, La, Fe and Co as essential component.Preferably representing Ca, La, composition formula as the atom ratio of the metallic element of A element, Fe and the Co of Ba and/or Sr: Ca 1-x-yla xa yfe 2n-z-wco zca win, the n of described 1-x-y, x, y, z, w and expression mol ratio meets
0.23≤(1-x-y+w)/(1+w)≤0.75、
0.2≤x/(1+w)≤0.65、
0≤y/(1+w)≤0.4、
0.2≤z/(1+w)＜0.65、
w≥0.025、
3 < n/ (1+w) < 6 Hes
0≤y/(1-x+w)＜0.56。
Described composition formula, represents with the atom ratio of metallic element, but contains the composition of oxygen (O), with composition formula: Ca 1-x-yla xa yfe 2n-z-wco zca wo α(wherein, the n of 1-x-y, x, y, z, w and α and expression mol ratio, meets
0.23≤(1-x-y+w)/(1+w)≤0.75、
0.2≤x/(1+w)≤0.65、
0≤y/(1+w)≤0.4、
0.2≤z/(1+w)＜0.65、
w≥0.025、
3 < n/ (1+w) < 6 Hes
0≤y/(1-x+w)＜0.56，
La and Fe are 3 valencys, and Ca, A element and Co are divalent, x=w+z and represent stoichiometric composition when n=6 than time, α=19.) represent.
In the composition of the described ferrite compounds containing oxygen (O), the atom ratio of oxygen, according to the valence mumber of Fe and Co, n value etc. and different.In addition in ferrite compounds, variation of the variation of the valence mumber of the Fe in room (Vacancy), the ferrite compounds of the oxygen when burning till in reducing atmosphere, the valence mumber of Co etc., causes oxygen to change for the ratio of metallic element.Therefore, the atom ratio α of actual oxygen has the situation that departs from 19.Therefore, in the present invention, to form the most specifically atom ratio of metallic element statement composition.
By taking ferrite compounds of the present invention as the main construct of ferrite sintered magnet,, using crystallization phases (thering is the ferrite phase of the M type magnetoplumbite type of hexagonal crystal) that ferrite compounds of the present invention was formed as principal phase, can obtain maintaining high B rwith high H k/ H cJstate under make H cJthe ferrite sintered magnet improving.Below, describe as the ferrite sintered magnet (following, to have the situation that is called " this ferrite sintered magnet ") of principal phase for the crystallization phases that ferrite compounds of the present invention is formed.
The principal phase of this ferrite sintered magnet, as described in, be the crystallization phases being formed by ferrite compounds of the present invention, be the ferrite phase with the M type magnetoplumbite type of hexagonal crystal.In general, magneticsubstance, particularly sintered magnet, be made up of multiple compounds, determines that the compound of the characteristic (physical property, magnet characteristic etc.) of this magneticsubstance is defined as " principal phase ".The principal phase of this ferrite sintered magnet, has the ferrite phase of the M type magnetoplumbite type of hexagonal crystal, also determines the essential part of physical property, the magnet characteristic etc. of this ferrite sintered magnet.
In this ferrite sintered magnet, except described principal phase, also contain the first Grain-Boundary Phase being present between two principal phases, and have three the second Grain-Boundary Phases between above principal phase.What is called is present in the first Grain-Boundary Phase between two principal phases, it is the Grain-Boundary Phase also referred to as " two particle Grain-Boundary Phases " in practitioner, refer in the time observing the cross section arbitrarily of ferrite sintered magnet, be present in the Grain-Boundary Phase that seems to be wire in the crystal boundary of principal phase and principal phase.In addition, what is called is present in three the second Grain-Boundary Phases between above principal phase, at the Grain-Boundary Phase that is called " multiple point Grain-Boundary Phase " etc. from the person that has come, refer in the time observing the cross section arbitrarily of ferrite sintered magnet, be present in it seems between three above principal phases and be nearly trilateral, closely Polygons or amorphous etc. Grain-Boundary Phase.Described the first Grain-Boundary Phase, its thickness is very thin, observes difficulty with X-ray diffraction pattern, is therefore preferably confirmed by the transmission electron microscope etc. with very high resolution.Further, in the following description, there is the situation of aggregate performance the first Grain-Boundary Phase and the second Grain-Boundary Phase, only have " Grain-Boundary Phase " the such situation that is called.
This ferrite sintered magnet, has described principal phase, described the first Grain-Boundary Phase and described the second Grain-Boundary Phase, preferably has as undertissue: in cross section arbitrarily, be scattered with described the second Grain-Boundary Phase, the average area of described the second Grain-Boundary Phase is lower than 0.2 μ m 2.In addition, in preferred mode, the second Grain-Boundary Phase has at 53 × 53 μ m in cross section arbitrarily 2scope in there are 900 above tissues.The average area of the second Grain-Boundary Phase, can try to achieve in the following way: the image for the reflection electronic picture (BSE picture) in the ferrite sintered magnet cross section from FE-SEM (field emission type scanning electronic microscope) carries out binary conversion treatment, try to achieve area and the number of the second Grain-Boundary Phase, make it add up to area divided by number.
[2] manufacture method of ferrite compounds
Ferrite compounds of the present invention, can form through manufacturing process shown below.Comprise following operation:
Mixing raw material powder, obtains the raw material powder mixed processes of mixing raw material powder;
Mixing raw material powder described in pre-burning, obtains the pre-burning operation of pre-burning body;
Pulverize described pre-burning body, obtain the pulverizing process of pre-burning body powder;
Burn till described pre-burning body powder, obtain the firing process of sintered body,
In described firing process, making the heat-up rate in the temperature range of 1100 DEG C～firing temperature is 1～4 DEG C/min, and to make the cooling rate in the temperature range of firing temperature～1100 DEG C be more than 6 DEG C/min.Further, when ferrite compounds of the present invention is used for to sintered magnet, between described pulverizing process and described firing process, can append the described pre-burning body powder that is shaped, obtain the forming process of molding etc.Describe for each operation below.
(a) raw material powder mixed processes
Ferrite compounds, concocts raw material powder as follows,, is representing Ca, La, composition formula as the atom ratio of the metallic element of A element, Fe and the Co of Ba and/or Sr: Ca that is 1-x-yla xa yfe 2n-z-wco zca win, make described 1-x-y, x, y, z, w and represent the n of mol ratio, meet
0.23≤(1-x-y+w)/(1+w)≤0.75、
0.2≤x/(1+w)≤0.65、
0≤y/(1+w)≤0.4、
0.2≤z/(1+w)＜0.65、
w≥0.025
3 < n/ (1+w) < 6 Hes
0≤y/(1-x+w)＜0.56。If outside the scope of the n of atom ratio and expression mol ratio in described regulation, can not get ferrite compounds of the present invention.
Further, La can replace its part with at least one of rare earth element of removing La.Replacement amount is preferably below 50% of La with molar ratio computing.Co also can replace its part with at least one that select from Zn, Ni and Mn.
No matter raw material powder valence mumber, can use oxide compound, carbonate, oxyhydroxide, nitrate, muriate of each metal etc.Also can be the solution that is dissolved with raw material powder.As the compound of Ca, can enumerate carbonate, oxide compound, muriate of Ca etc.As the compound of La, can enumerate La 2o 3deng oxide compound, La (OH) 3deng oxyhydroxide, La 2(CO 3) 38H 2the carbonate of O etc. etc.As the compound of A element, can enumerate carbonate, oxide compound, muriate of Ba and/or Sr etc.As the compound of iron, can enumerate ferric oxide, ironic hydroxide, iron(ic) chloride, roll scale etc.As the compound of Co, can enumerate CoO, Co 3o 4deng oxide compound, CoOOH, Co (OH) 2, Co 3o 4m 1h 2o (m 1for positive number) etc. oxyhydroxide, CoCO 3deng carbonate, and m 2coCO 3m 3co (OH) 2m 4h 2slag carbonate (the m of O etc. 2, m 3, m 4for positive number).
CaCO 3, Fe 2o 3and La 2o 3raw material powder in addition, adds can mix from raw material time, also can after pre-burning, add.For example, (1) can concoct CaCO 3, Fe 2o 3, La 2o 3and Co 3o 4, mix and pre-burning after, pulverizing pre-burning body, burns till and manufactures ferrite compounds, (2) also can concoct CaCO 3, Fe 2o 3and La 2o 3, after mixing and pre-burning, in pre-burning body, add Co 3o 4, pulverize and burn till and manufacture ferrite compounds.
Reaction during for pre-burning promotes, also can add as required and contain B 2o 3, H 3bO 3deng about compound to 1 quality % of B.Because H 3bO 3also have and burning till the effect of shape and size of time control combinations grain, so can (before Crushing of Ultrafine and before burning till) add after pre-burning, also can before pre-burning and after pre-burning, this two side add.
Mix each raw material powder of preparing, become mixing raw material powder.The mixing of raw material powder, with any of wet type and dry type.If stir with together with the media of steel ball etc., mixing raw material powder more equably.In the situation of wet type, dispersion medium preferably makes water.For the dispersed object that improves raw material powder, also can use the known dispersion agent of poly carboxylic acid ammonium, calcium gluconate etc.The directly pre-burning of former slip mixing, pre-burning again after also can dewatering for former slip.
(b) pre-burning operation
By the mixing raw material powder that dry type is mixed or wet mixing obtains, use the heating such as electric furnace, gas furnace, by solid state reaction, form the ferrite compounds of the M type magnetoplumbite type of hexagonal crystal.This process is called " pre-burning ", and the compound obtaining is called " pre-burning body ".The ferrite compounds forming with pre-burning, is the presoma of ferrite compounds of the present invention, and in this stage, crystalline texture is sufficient stabilization not, has 2a, 4e, 4f in the unit cell that is present in M type magnetoplumbite type 1, 4f 2total amount with the Ca of the brilliant position of 12k, does not reach 0.05 above situation in per unit structure cell.
Pre-burning operation is preferably to carry out in more than 5% atmosphere at oxygen concn.If oxygen concn is lower than 5%, exaggerated grain growth, causes the generation of out-phase etc.Preferred oxygen concn is more than 20%.
In pre-burning operation, form the solid state reaction of ferrite compounds along with the rising of temperature is carried out together, about 1100 DEG C complete.Calcined temperature is during lower than 1100 DEG C, and unreacted rhombohedral iron ore (ferric oxide) is remaining, is not therefore preferred.On the other hand, if calcined temperature exceedes 1450 DEG C, excessive grain growth therefore need to spend very many time in pulverizing process on pulverizing.Therefore, preferably calcined temperature is 1100～1450 DEG C, more preferably 1200～1350 DEG C.Preferably the pre-burning time is 0.5～5 hour.
Before pre-burning, add H 3bO 3time, because Ferrite method reaction is promoted, so can carry out pre-burning with 1100 DEG C～1300 DEG C.
(c) interpolation of sintering aid
When ferrite compounds of the present invention is used for to sintered magnet, as sintering aid, preferably after described pre-burning operation, before forming process described later, in pre-burning body or pre-burning body powder, with respect to pre-burning body or pre-burning body powder 100 quality % and add the SiO of 0～1.8 quality % 2, and be scaled the CaCO of 0～2 quality % with CaO 3.The interpolation of sintering aid can adopt as inferior method, for example, adds sintering aid and implement pulverizing process afterwards again in the pre-burning body being obtained by pre-burning operation; In the way of pulverizing process, add sintering aid; Or in pre-burning body after pulverizing process, add, implement again forming process after mixed sintering auxiliary agent.
Further, in the present invention, CaCO 3addition all with CaO convert explain.The addition converting according to CaO, CaCO 3addition, can try to achieve by following formula:
(CaCO 3the addition that converts of molecular weight × CaO) molecular weight of/CaO.
For example, convert with CaO, add the CaCO of 1.5 quality % 3time, for (nucleidic mass of 40.08[Ca] nucleidic mass of+12.01[C] nucleidic mass × 3 of+48.00[O]=100.09[CaCO 3molecular weight]) addition that converts with CaO of × 1.5 quality %[]/(nucleidic mass of 40.08[Ca] nucleidic mass of+16.00[O] molecular weight of=56.08[CaO])=2.677 quality %[CaCO 3addition].
In CaLaCo ferrite, because contain Ca as principal phase composition, so, even if do not add SiO 2and CaCO 3as sintering aid, liquid phase also can generate and carry out sintering., even if be not added on the main described SiO that forms Grain-Boundary Phase in ferrite sintered magnet 2and CaCO 3, Grain-Boundary Phase still can form.On the other hand, add SiO as sintering aid 2and CaCO 3time, the part that it becomes liquid composition in the time of sintering, becomes Grain-Boundary Phase after sintering.
Except above-mentioned SiO 2and CaCO 3in addition, after pre-burning operation, before forming process described later, can add Cr 2o 3, A1 2o 3deng.Its addition is preferably respectively below 5 quality %.
(d) pulverizing process
Pre-burning body is pulverized by vibrating mill, ball mill, attritor etc., becomes pre-burning body powder.Preferably the mean particle size of pre-burning body powder reaches 0.4～0.8 μ m left and right (air permeability method).Pulverizing process be dry type pulverize and case of wet attrition any all can, preferably combination both sides carry out.
Case of wet attrition, carries out water and/or non-water solvent (organic solvents of acetone, ethanol, dimethylbenzene etc.) as dispersion medium.By case of wet attrition, generate the slurry that is mixed with dispersion medium and pre-burning body powder.Preferably, in slurry, add known dispersion agent and/or the tensio-active agent of 0.2～2 quality % with solids component ratiometer.After case of wet attrition, preferably concentrate and mix for slurry.
In the pre-burning body powder of pulverizing, because contain, dehydration property in exaggerated grain growth and the forming process that causes the ferrite particle occurring in firing process worsens and the super-fine powder lower than 0.1 μ m of cacoplastic reason, so in order to remove these super-fine powder, preferably implement thermal treatment for the pre-burning body powder of pulverizing.Preferably having implemented heat treated powder pulverizes once again.So, by adopting the pulverizing process (hereinafter referred to as " thermal treatment is pulverizing process again ") being formed by following operation, that is: the first Crushing of Ultrafine operation, for the powder being obtained by described the first Crushing of Ultrafine operation implement heat treated operation, for the second Crushing of Ultrafine operation of having implemented described heat treated powder and pulverizing once again, thus, when ferrite compounds of the present invention is used for to sintered magnet, can make the H of this ferrite sintered magnet cJimprove.
In common pulverizing process, inevitably produce lower than the super-fine powder of 0.1 μ m, due to the existence of this super-fine powder, cause occurring the exaggerated grain growth of ferrite particle in firing process, H cJreduce, or in forming process dehydration property variation, or molding produce bad, due to dehydration to spend a large amount of time, cause extrusion cycle reduce.If implement thermal treatment for the powder that contains the super-fine powder being obtained by the first Crushing of Ultrafine operation, between the larger powder of particle diameter and super-fine powder, react, can reduce the amount of super-fine powder.Then, carry out removing of granularity adjustment and necking down (necking) by the second Crushing of Ultrafine operation, make the powder of designated size.Thus, the amount that can obtain super-fine powder is few, and the powder of size-grade distribution excellence can suppress the exaggerated grain growth of the ferrite particle in firing process, when ferrite compounds of the present invention is used for to sintered magnet, can make the H of this ferrite sintered magnet cJimprove, and can solve the above-mentioned problem in forming process.
If utilize the thermal treatment H that pulverizing process brings again cJraising effect, set greatlyr (for example mean particle size 0.8～1.0 μ m (air permeability method) left and right) even if the second Crushing of Ultrafine operation is formed to the particle diameter of powder, also can obtain H equal when using the powder (about mean particle size 0.4～0.8 μ m (air permeability method)) being obtained by common pulverizing process cJ.Therefore, the time shorten of the second Crushing of Ultrafine operation can be realized, and the further raising of dehydration property, the raising of extrusion cycle can be realized.
So, according to thermal treatment pulverizing process again, although can obtain various favourable parts, follow manufacturing process increase and come cost rise can not avoid.But, the above-mentioned improved effect that adopts thermal treatment to obtain when pulverizing process again, with do not adopt thermal treatment again when pulverizing process compared with, be large in the extreme, therefore can offset described cost and rise.Therefore, in the present invention, thermal treatment again pulverizing process is also significant operation in practical.
The first Crushing of Ultrafine, the same with aforementioned common pulverizing, use vibrating mill, jet-type disintegrating machine, ball mill, attritor etc. to carry out.The mean particle size of the powder after pulverizing is preferably 0.4～0.8 μ m left and right (air permeability method).Pulverizing process with dry type pulverize and case of wet attrition any all can, preferably combination both sides carry out.
The thermal treatment of carrying out after the first Crushing of Ultrafine operation, preferably carries out with 600～1200 DEG C, more preferably carries out with 800～1100 DEG C.The heat treated time is not particularly limited, but be preferably 1 second～100 hours, more preferably about 1～10 hour.
The second Crushing of Ultrafine carrying out after heat treatment step is the same with the first Crushing of Ultrafine, uses vibrating mill, jet-type disintegrating machine, ball mill, attritor etc. to carry out.Because obtained substantially the particle diameter of expecting in the first Crushing of Ultrafine operation, so in the second Crushing of Ultrafine operation, be mainly to carry out removing of granularity adjustment and necking down.Therefore, preferably alleviate pulverization conditions by shortening grinding time than the first Crushing of Ultrafine operation.If pulverize with the condition of degree with the first Crushing of Ultrafine operation, generate once again super-fine powder, be not therefore preferred.
Obtain higher H if wanted than this ferrite sintered magnet obtaining via common pulverizing process cJthe same with common pulverizing process, preferably the mean particle size of the powder after the second Crushing of Ultrafine reaches 0.4～0.8 μ m left and right (air permeability method), if want effectively to utilize the favourable part of further raising, the further raising of extrusion cycle etc. of time shorten, the dehydration property of pulverizing process, reach 0.8～1.2 μ m, preferably reach 0.8～1.0 μ m left and right (air permeability method).
(e) forming process
When ferrite compounds of the present invention is used for to sintered magnet, will remove dispersion medium for the slurry after pulverizing process on one side, in Zhong Huowu magnetic field, magnetic field, carry out extrusion molding on one side.Particularly, by carry out extrusion molding in magnetic field, can make the crystalline orientation of powder particle aim at (orientation), can make the magnet characteristic of ferrite sintered magnet improve tremendously.In addition,, in order to make directed raising, also can add respectively dispersion agent and lubricant 0.01～1 quality %.Also can before shaping, concentrate as required in addition slurry.Concentrated except natural subsidence, preferably undertaken by centrifugation, press filtration etc.
(f) firing process
The pre-burning body powder being obtained by pulverizing process, or the molding being obtained by forming process, as required after degreasing, then burn till (sintering).Obtain thus sintered body (sintered magnet).In firing process, making the heat-up rate in the temperature range of 1100 DEG C～firing temperature is 1～4 DEG C/min, and to make the cooling rate in the temperature range of firing temperature～1100 DEG C be more than 6 DEG C/min.Thus, can produce 2a, 4e, the 4f in the unit cell of the M type magnetoplumbite type that is present in hexagonal crystal 1, 4f 2with in the total amount per unit structure cell of the Ca of the brilliant position of 12k, be 0.05 above ferrite compounds.
Heat-up rate is lower than 1 DEG C/min, for example 0.5 DEG C/min, also can obtain ferrite compounds of the present invention, if but heat-up rate is too slow, the production cycle elongated, and cause the increase of production cost, be not therefore preferred.Therefore, preferably heat-up rate is 1～4 DEG C/min.Preferred heat-up rate is 1～2 DEG C/min.In addition, if cooling rate is that more than 6 DEG C/min the upper limit does not have special stipulation, but in order to make it fast cooling, in firing furnace, need cooling apparatus and blast apparatus, therefore likely cause the increase of production cost.If consider this some, preferably cooling rate on be limited to 10 DEG C/min of left and right.
The temperature range that makes heat-up rate reach 1～4 DEG C/min is 1100 DEG C～firing temperature.Temperature province more than 1100 DEG C, if heat-up rate exceedes 4 DEG C/min, even temporary transient, also has the possibility that can not get ferrite compounds of the present invention.Further, if the heat-up rate in the temperature range of 1100 DEG C～firing temperature in 1～4 DEG C/min, the heat-up rate at the temperature beyond it is not particularly limited.In order to make the heat-up rate in the temperature range of 1100 DEG C～firing temperature reach 1～4 DEG C/min, preferably than 1100 DEG C of low temperature, for example 800 DEG C above, lower than the temperature provinces of 1100 DEG C, also make in advance heat-up rate reach 1～4 DEG C/min.
Making cooling rate reach 6 DEG C/min of above temperature ranges is firing temperature～1100 DEG C.Temperature province more than 1100 DEG C, if cooling rate, lower than 6 DEG C/min, even temporary transient, still has the possibility that can not get ferrite compounds of the present invention.Further, if the cooling rate in the temperature range of firing temperature～1100 DEG C reaches more than 6 DEG C/min, the cooling rate of the temperature beyond it is not particularly limited.
Burn till and use electric furnace, gas furnace etc. to carry out.Burning till is preferably to carry out in more than 10% atmosphere at oxygen concn.If oxygen concn lower than 10%, has the possibility of the generation that exaggerated grain growth and out-phase occur, be difficult to use in sintered magnet, bonded permanent magnet, magnetic recording medium etc.Oxygen concn is more preferably more than 20%, and most preferably 100%.Firing temperature is preferably 1150～1250 DEG C.Firing time is preferably 0.5～2 hour.The average crystallite particle diameter of the sintered body (sintered magnet) being obtained by firing process is about 0.5～2 μ m.
The sintered body being obtained by described firing process is pulverized (fragmentation) as required, thereby can mainly be contained the powder of the crystallization phases being formed by ferrite compounds of the present invention, use it for bonded permanent magnet, magnetic recording medium etc., can improve its performance.In addition, after having carried out described forming process, the sintered magnet being obtained by described firing process, can directly use as ferrite sintered magnet using this state., this ferrite sintered magnet is taking crystallization (having the ferrite phase of the M type magnetoplumbite type of hexagonal crystal) that ferrite compounds of the present invention was formed as principal phase.
The manufacture method of ferrite compounds of the present invention is characterised in that following main points: burning till in (sintering) operation, make slowly (1～4 DEG C/min) of heat-up rate of 1100 DEG C～firing temperature, make the cooling rate of firing temperature～1100 after burning till DEG C than heat-up rate fast (more than 6 DEG C/min).Thus, can obtain 2a, 4e, the 4f in the unit cell of the M type magnetoplumbite type that is present in hexagonal crystal 1, 4f 2with in the total amount per unit structure cell of the Ca of the brilliant position of 12k, be 0.05 above ferrite compounds, taking this ferrite compounds in the ferrite sintered magnet of main composition thing, can maintain high B rwith high H k/ H cJstate under make H cJimprove.Below set forth the reason that the present inventors infer, but this reason according to present income to conclusion infer, not attempt to limit technical scope of the present invention.
The firing process of general ferrite sintered magnet is classified as liquid phase sintering.In the manufacture method of described ferrite compounds of the present invention, add SiO as sintering aid 2and CaCO 3time, this sintering aid becomes a part for liquid composition in the time burning till, and in the time not adding sintering aid, a part for principal phase forms liquid phase in the time burning till.These liquid phases, after burning till, become the first Grain-Boundary Phase being present between two principal phases, and are present in three the second Grain-Boundary Phases between above principal phase.
In the manufacture method of ferrite compounds of the present invention, it is 1～4 DEG C/min by making the heat-up rate in the temperature range of 1100 DEG C～firing temperature, at leisure by this temperature province, can promote solid phase to the dissolving of liquid phase and separate out, and in the crystallization of M type magnetoplumbite type, each atom moves to the position that makes crystalline texture more stable.Consequently, among the brilliant position that 24 Fe that exist and Co occupy, there is 0.05 to be replaced by Ca above in the per unit structure cell of M type magnetoplumbite type, that is, be present in 2a, 4e, 4f in the unit cell of M type magnetoplumbite type 1, 4f 2with in the total amount per unit structure cell of the Ca of the brilliant position of 12k, be more than 0.05.Think thus, the unbalanced of the distortion of crystalline texture and charge balance relaxed, as the crystalline texture stabilization of M type magnetoplumbite type.
But, when cooling after burning till, if the same when heating up, at leisure by 1100 DEG C of temperature provinces to firing temperature, there is once again solid phase to the dissolving of liquid phase and separate out, and the movement of atom in the crystallization of M type magnetoplumbite type, the crystalline texture of stabilization is destroyed.Therefore, be more than 6 DEG C/min by making the cooling rate in the temperature range of firing temperature～1100 DEG C, rapidly by this temperature province, think and can former state keep the stable crystalline texture forming while intensification.
In firing process, solid phase is to the dissolving of liquid phase with separate out, and the movement of atom in the crystallization of M type magnetoplumbite type, thinks that not only CaLaCo ferrite can occur, and SrLaCo ferrite also can occur.But CaLaCo ferrite and SrLaCo ferrite differ widely on following point.
As described in, in CaLaCo ferrite, as sintering aid add SiO 2and CaCO 3time, this sintering aid forms liquid phase in the time burning till, and while not adding sintering aid, a part for principal phase forms liquid phase in the time burning till.In other words, the both sides of principal phase and liquid phase are contained Ca.So think, in firing process, solid phase to the dissolving of described liquid phase and separate out occur time, the contained Ca of the Ca that principal phase is contained and liquid phase moves mutually.That is, be promoted because the mutual movement of the Ca between principal phase and liquid phase causes solid phase to the dissolving of liquid phase and separates out, its result thinks, in the ferritic crystalline texture of CaLaCo, the displacement of a part for the brilliant position that Ca occupies Fe or Co is promoted.
On the other hand, in SrLaCo ferrite, principal phase is not containing Ca substantially.Therefore, in the time burning till, the SiO adding as sintering aid 2and CaCO 3the main liquid phase that forms, different from CaLaCo ferrite, in the time not adding sintering aid, in the preferred firing range of 1200 DEG C of neighborhoods, form hardly liquid phase.Inventors (add the SiO of 1.2 quality % at SrLaCo ferrite sintered magnet as sintering aid 2with the CaCO that is scaled 1.5 quality % with CaO 3) in, utilize scanning transmission electron microscope (STEM) and be equipped with the FE-TEM of X-ray energy spectrometer (EDS) function, when the composition of three Grain-Boundary Phases carries out point analysis arbitrarily, obtain the result shown in table 1.Further, the unit of content is all atom %.
Table 1
Metallic element Grain-Boundary Phase 1 Grain-Boundary Phase 2 Grain-Boundary Phase 3
Ca 35.3 36.6 35.0
Si 38.2 39.8 42.6
Sr 10.8 10.4 9.3
La 1.6 1.5 1.3
Fe 14.1 11.7 11.8
As shown in table 1, in the Grain-Boundary Phase of SrLaCo ferrite sintered magnet, except the Si, the Ca that add as sintering aid, also contain Sr, La, Fe.Result is thought thus, in SrLaCo ferrite, solid phase to the dissolving of described liquid phase and separate out occur time, principal phase dissolve, principal phase composition moves to liquid phase.
There is the stability of the crystalline texture of the M type magnetoplumbite type of hexagonal crystal, known Sr ferrite > SrLaCo ferrite > CaLaCo ferrite.Why as described in think that contained Ca and the contained Ca of liquid phase of principal phase moves mutually in CaLaCo ferrite, the ferritic crystalline texture of CaLaCo do not have Sr ferrite and SrLaCo ferrite stable be also an essential factor.Therefore think, in the stable SrLaCo ferrite of crystalline texture, even if principal phase is dissolved, principal phase composition moves to liquid phase, and liquid composition also can not move to principal phase.Think exactly stable SrLaCo ferrite to there is no fear of mutually absorbing Ca and become unsure state.Therefore think, in SrLaCo ferrite, solid phase is to the dissolving of described liquid phase and separate out while generation, between principal phase and liquid phase, can mutually not move, and the Sr of principal phase composition and La move to liquid phase unilaterally.The Sr of principal phase composition and La are to liquid phase dissolved, and from principal phase shell stripping Sr and La, the spinel that remaining crystallization magneticanisotropy is low is constructed, and this is considered to the essential factor of the crystallization magneticanisotropy reduction that forms principal phase interface neighborhood.
In ferrite compounds of the present invention, in described manufacturing processed, the composition of ferrite compounds is also mobile to Grain-Boundary Phase (liquid phase).But as described in, in CaLaCo ferrite, the both sides of ferrite compounds and liquid phase are contained Ca, due to the mutual movement of the Ca between ferrite compounds and liquid phase, make solid phase to the dissolving of liquid phase and separate out to be promoted, and therefore think that crystalline texture obtains stabilization.
So, in CaLaCo ferrite and SrLaCo ferrite, solid phase is to the dissolving of liquid phase and separate out while generation, thinks different phenomenons can occur.Therefore think, in SrLaCo ferrite, can be as ferrite compounds of the present invention, be formed among the brilliant position that 24 Fe existing in the per unit structure cell of M type magnetoplumbite type and Co occupy, there is 0.05 above by the such crystalline texture of the displacement of Ca, such crystalline texture, the CaLaCo ferrite that is considered to contain as principal constituent certain above Ca is peculiar, or just can significantly present in CaLaCo ferrite.
[embodiment]
Below, the embodiment when main composition thing using ferrite compounds of the present invention as ferrite sintered magnet is described, but the present invention is not limited by it.
Embodiment 1
The composition formula of atom ratio representing metallic element: Ca 1-x-yla xa yfe 2n-z-wco zca win, to reach the mode of (1-x-y+w)/(1+w)=0.5, x/ (1+w)=0.5, y/ (1+w)=0, y/ (1-x+w)=0, z/ (1+w)=0.3, n/ (1+w)=5.2 and w=0.1, prepare blending CaCO 3powder, La (OH) 3powder, Fe 2o 3powder and Co 3o 4the raw material powder that powder forms, mixes 4 hours with wet-type ball mill, dry and become whole grain.Then, in atmosphere, with 1300 DEG C of pre-burnings 3 hours, carry out coarse reduction with beater grinder for the pre-burning body being obtained, obtain meal flour.
For described meal flour 100 quality %, add the SiO shown in table 2 2and CaCO 3(CaO scaled value), so that water is carried out to Crushing of Ultrafine as the wet-type ball mill of dispersion medium, until the mean particle size of being measured by air permeability method reaches 0.55 μ m.For obtained Crushing of Ultrafine slurry, remove dispersion medium on one side, make on one side compression aspect parallel with field direction and apply the magnetic field of about 1.3T, with the pressure forming of about 50MPa, obtain multiple columned moldinies (being axially field direction).
The molding obtaining is packed in firing furnace, in atmosphere, burn till with the heat-up rate shown in table 2 and cooling rate, obtain ferrite sintered magnet (test portion No.1～26).Heat-up rate described in table 2 and cooling rate, what show respectively is 1100 DEG C of heat-up rates to 1210 DEG C (firing temperatures), with 1210 DEG C (firing temperatures) cooling rate to 1100 DEG C, burn till at 1210 DEG C (firing temperature) and keep 1 hour and carry out.Carry out with 7.5 DEG C/min from the intensification of room temperature to 1100 DEG C in addition, cooling from 1100 DEG C to room temperature, by cutting off the power supply of firing furnace, opens the fire door of firing furnace and carries out.
Table 2
Figure BDA00003237492600181
Note 1: the heat-up rate from 1100 DEG C to 1210 DEG C (firing temperatures)
Note 2: the cooling rate from 1210 DEG C (firing temperatures) to 1100 DEG C
The B of the ferrite sintered magnet of test portion No.1～8 rand H cJmeasuring result be presented in Fig. 1, H k/ H cJmeasuring result be presented in Fig. 2.In Fig. 1, the plotting of bullet represents B rvalue, the plotting of black triangle represents H cJvalue.Further, at H k/ H cJin, H kthat J becomes 0.95J in the second quadrant of J (magnetized size)-H (intensity in magnetic field) curve rthe value (same below) of H of position of value.
The B of the ferrite sintered magnet of test portion No.9～18 rand H cJmeasuring result be presented in Fig. 3, H k/ H cJmeasuring result be presented in Fig. 4.In Fig. 3, solid line represents B rvalue, dotted line represents H cJvalue.In Fig. 3 and Fig. 4, the plotting of bullet represents that heat-up rate is the test portion (No.9～13) of 1 DEG C/min, and the plotting of black triangle represents that heat-up rate is the test portion (No.14～18) of 4 DEG C/min.
The B of the ferrite sintered magnet of test portion No.19～26 rand H cJmeasuring result be presented in Fig. 5, H k/ H cJmeasuring result be presented in Fig. 6.In Fig. 5, the plotting of bullet represents B rvalue, the plotting of black triangle represents H cJvalue.
As depicted in figs. 1 and 2, at the SiO that is added with 0.6 quality % 2with the CaCO that is scaled 0.7 quality % with CaO 3test portion (No.1～8) in, when to make heat-up rate be the scope of 1～4 DEG C/min, although B rand H k/ H cJthere are some to reduce, but H cJsignificantly improve H k/ H cJmaintain more than 85%.
As shown in Figure 3 and Figure 4, add the SiO of 0.6 quality % 2with the CaCO that is scaled 0.7 quality % with CaO 3, heat-up rate is that the test portion (No.9～13) of 1 DEG C/min and heat-up rate are the test portion (No.14～18) of 4 DEG C/min, is when more than 6 DEG C/min making cooling rate, B rthere are some to improve, H cJsignificantly improve.In addition, H k/ H cJmaintain more than 85%.Heat-up rate be a side of the test portion (No.9～13) of 1 DEG C/min be 4 DEG C/min with heat-up rate test portion (No.9～13) compared with, B rand H k/ H cJthere are on the whole some raisings.
As shown in Figure 5 and Figure 6, at the SiO that is added with 1.2 quality % 2with the CaCO that is scaled 1.5 quality % with CaO 3test portion (No.19～26) in, make heat-up rate in the time of the scope of 1 DEG C/min to 4 DEG C/min, almost do not find B rreduction, H cJsignificantly improve, can obtain exceeding the high value of not reaching so far of 500kA/m (about 6.3kOe).Although H k/ H cJa shade below 85%, but still maintain high value.
Next, pulverize test portion No.3,6,8,9,13 and 24, obtain sintered compact comminuted powder.Obtained sintered compact comminuted powder is filled in the Lindemann glass kapillary (リ Application デ マ Application ガ ラ ス キ ヤ ピ ラ リ mono-) of internal diameter 0.1mm, debye-Scherrer photographic camera (デ バ イ=シ エ ラ mono-カ メ ラ) that use is arranged at the BL19B2 of SPring-8, carries out powder x-ray diffraction measurement.Incident X-rays energy is 20keV, and detector uses imaging plate, and 5 minutes time shutter, measurement temperature is room temperature.Use RIETAN-FP, carry out the analysis of Li Te Wald for obtained diffraction is linear, try to achieve the brilliant position of Fe (2a, 4e, 4f in the unit cell of the M type magnetoplumbite type (to fall M type) that is present in hexagonal crystal 1, 4f 2with the brilliant position of 12k) the total amount (Ca of Ca fe).Further, in Ben Lite Wald is analyzed, about Ca and La, try to achieve and occupy brilliant position and occupation rate, but do not carry out the differentiation of Fe and Co, as imaginary element processing of the same race.
Test portion No.3,6,8,9,13 and 24 Ca feanalytical results, and according to Ca fethe expression Ca, the La that calculate, as the composition formula of the atom ratio of the metallic element of A element, Fe and the Co of Ba and/or Sr: Ca 1-x-yla xa yfe 2n-z-wco zca win, 1-x-y, x, y, z, w, n, (1-x-y+w)/(1+w), x/ (1+w), y/ (1+w), z/ (1+w), n/ (1+w) and y/ (1-x+w) are presented in table 3.Also have, the result of being analyzed by Ben Lite Wald, exist the kind of the brilliant position of Fe of Ca and the occupation rate of the Ca of brilliant figure place and each brilliant position can not be specifically for one, although can get brilliant the situation for 2d and 12k that has Ca, and be the crystalline texture models such as the situation of 2d, 2a and 4e, but the Ca shown in table 3 fe, the mean value of the total amount of the Ca of the brilliant position of Fe in the crystalline texture model unit cell that try to achieve, that be present in M type magnetoplumbite type that represents can set up with the result of analyzing according to these Li Te Walds respectively.For example, if be test portion No.3, the crystalline texture model that can set up according to the result of Li Te Wald analysis is 16 kinds, the total amount of the Ca of the brilliant position of Fe in the unit cell that is present in M type structure of each crystalline texture model is 0.12～0.14/u.c. (u.c.:unit cell), is Ca as 0.14/u.c. of its mean value fevalue.
Table 3
(connecing table 3)
Figure BDA00003237492600211
As shown in table 3, be 1～4 DEG C/min at heat-up rate, and cooling rate is in 6 DEG C/min of above test portion No.3,6,13 and 24 ferrite sintered magnet (inventive example), Ca febe respectively 0.14/u.c., 0.12/u.c., 0.14/u.c. and 0.07/u.c..On the other hand, be 6 DEG C/min and heat-up rate is the test portion No.8 of 6.67 DEG C/min in cooling rate as a comparative example, and heat-up rate is that 1 DEG C/min and cooling rate are in the test portion No.9 of 1 DEG C/min, known Ca fefew to 0.02/u.c. and 0.04/u.c. respectively.
As above, the ferrite sintered magnet using ferrite compounds of the present invention as main composition thing, can maintain high B rwith high H k/ H cJstate under make H cJimprove, therefore also can fully tackle slimming.
Embodiment 2
The composition formula of atom ratio representing metallic element: Ca 1-x-yla xa yfe 2n-z-wco zca win, n/ (1+w)=5.3, concocts Ba as A element (y) in the mode shown in table 4, for meal flour 100 quality %, adds the SiO of 0.6 quality % 2with the CaCO that is scaled 0.7 quality % with CaO 3, making firing temperature is 1200 DEG C, according to the heat-up rate shown in table 4 and cooling rate, in addition, all obtains the ferrite sintered magnet of test portion No.27～31 in the mode identical with embodiment 1.Also have as Ba raw material, use BaCO 3powder.The B of the ferrite sintered magnet obtaining r, H cJand H k/ H cJmeasuring result be presented in table 5.In addition, similarly to Example 1, analyze the Ca trying to achieve by Li Te Wald feanalytical results, and by Ca fethe expression Ca, the La that calculate, as the composition formula of the atom ratio of the metallic element of A element, Fe and the Co of Ba and/or Ba: Ca 1-x-yla xa yfe 2n-z-wco zca win, 1-x-y, x, y, z, w, n, (1-x-y+w)/(1+w), x/ (1+w), y/ (1+w), z/ (1+w), n/ (1+w) and y/ (1-x+w) are presented in table 6.
Table 4
Note 1: the heat-up rate from 1100 DEG C to 1200 DEG C (firing temperatures)
Note 2: the cooling rate from 1200 DEG C (firing temperatures) to 1100 DEG C
Table 5
Table 6
Figure BDA00003237492600223
(connecing table 6)
Figure BDA00003237492600224
From table 5 and table 6, heat-up rate is from 1 DEG C/min to 4 DEG C/min, and cooling rate is the ferrite sintered magnet (inventive example) of 6 DEG C/min of above test portion No.27～29, while containing A element, and Ca fealso be respectively 0.11/u.c., 0.13/u.c. and 0.11/u.c., there is high B rwith high H cJwith high H k/ H cJ.On the other hand, be 1 DEG C/min and cooling rate is the test portion No.30 of 1 DEG C/min at heat-up rate as a comparative example, and cooling rate is that 6 DEG C/min and heat-up rate are in the test portion No.31 of 6.67 DEG C/min, Ca fefew to 0.04/u.c. and 0.03/u.c., known H respectively cJand H k/ H cJlow.
Embodiment 3
The composition formula of atom ratio representing metallic element: Ca 1-x-yla xa yfe 2n-z-wco zca win, making elements A is Sr, concoct (1-x-y+w)/(1+w), x/ (1+w), y/ (1+w), y/ (1-x+w), z/ (1+w) and n/ (1+w) in the mode shown in table 7, making firing temperature is 1200 DEG C, according to the heat-up rate shown in table 7, cooling rate, all obtain in addition the ferrite sintered magnet of test portion No.32～36 in mode similarly to Example 1.Also have as Sr raw material and use SrCO 3.The B of the ferrite sintered magnet obtaining r, H cJand H k/ H cJmeasuring result be presented in table 8.In addition, similarly to Example 1, analyze the Ca trying to achieve by Li Te Wald feanalytical results, and by Ca fethe expression Ca, the La that calculate, as the composition formula of the atom ratio of the metallic element of A element, Fe and the Co of Ba and/or Sr: Ca 1-x-yla xa yfe 2n-z-wco zca win, 1-x-y, x, y, z, w, n, (1-x-y+w)/(1+w), x/ (1+w), y/ (1+w), z/ (1+w), n/ (1+w) and y/ (1-x+w) are presented in table 9.
Table 7
Figure BDA00003237492600231
(connecing table 7)
Figure BDA00003237492600241
Note 1: the heat-up rate from 1100 DEG C to 1200 DEG C (firing temperatures)
Note 2: the cooling rate from 1200 DEG C (firing temperatures) to 1100 DEG C
Table 8
Figure BDA00003237492600242
Table 9
(connecing table 9)
Figure BDA00003237492600244
From table 8 and table 9, heat-up rate from 1 DEG C/min to 4 DEG C/min and cooling rate be more than 6 DEG C/min, y/ (1-x+w) is lower than the ferrite sintered magnet (inventive example) of 0.56 test portion No.32, Ca febe 0.12/u.c., demonstrate high B rwith high H cJwith high H k/ H cJ.On the other hand, it is 1 DEG C/min and cooling rate is the test portion No.33 of 1 DEG C/min at heat-up rate as a comparative example, cooling rate is 6 DEG C/min and heat-up rate is the test portion No.34 of 6.67 DEG C/min, heat-up rate is that 1 DEG C/min to 4 DEG C/min and cooling rate are more than 6 DEG C/min, the test portion No.35 of y/ (1-x+w)=0.672 simultaneously, and in the test portion No.36 of y/ (1-x+w)=1.000, Ca fefew to 0.03/u.c., 0.03/u.c., 0.02/u.c. and 0.00/u.c., known H respectively cJand H k/ H cJlow.
Embodiment 4
The composition formula of atom ratio representing metallic element: Ca 1-x-yla xa yfe 2n-z-wco zca win, making elements A is Sr (SrCO 3), concoct (1-x-y+w)/(1+w), x/ (1+w), y/ (1+w), y/ (1-x+w), z/ (1+w) and n/ (1+w) in the mode shown in table 10, raw material powder for formation like this carries out pre-burning, pulverizes similarly to Example 1 this pre-burning body.With 150 DEG C of dry Crushing of Ultrafine slurry 8h that obtained, for the micro mist flour obtaining by the sieve aperture of mesh 100 μ m, with the heat-up rate shown in table 10 and cooling rate, making firing temperature is 1200 DEG C, all identical with embodiment 1 and burn till in addition.The sintered body obtaining with agate mortar fragmentation, the ferrite that obtains test portion No.37～39 burns till powder.
Table 10
Figure BDA00003237492600251
(connecing table 10)
Figure BDA00003237492600252
Note 1: the heat-up rate from 1100 DEG C to 1200 DEG C (firing temperatures)
Note 2: the cooling rate from 1200 DEG C (firing temperatures) to 1100 DEG C
The ferrite obtaining burns till the saturation magnetization σ of powder sand H ameasuring result be presented in table 11.In addition, similarly to Example 1, analyze the Ca trying to achieve by Li Te Wald feanalytical results, and by Ca fethe expression Ca, the La that calculate, as the composition formula of the atom ratio of the metallic element of A element, Fe and the Co of Sr: Ca 1-x-yla xa yfe 2n-z-wco zca win, 1-x-y, x, y, z, w, n, (1-x-y+w)/(1+w), x/ (1+w), y/ (1+w), z/ (1+w), n/ (1+w) and y/ (1-x+w) are presented in table 12.
Table 11
Figure BDA00003237492600261
Table 12
Figure BDA00003237492600262
(connecing table 12)
Figure BDA00003237492600263
From table 11 and table 12, heat-up rate is 1 DEG C/min, and cooling rate is that the ferrite of the test portion No.37 of 6 DEG C/min burns till powder (inventive example), Ca febe 0.14/u.c., demonstrate high σ swith high H a.On the other hand, be 6 DEG C/min and heat-up rate is the test portion No.38 of 6.67 DEG C/min in cooling rate as a comparative example, heat-up rate is that 1 DEG C/min and cooling rate are 6 DEG C/min, in the test portion No.39 of y/ time (1-x+w)=1.0, Ca fefew to 0.03/u.c. and 0.00/u.c., σ respectively sand H alow.
[utilizability in industry]
Ferrite compounds of the present invention, by for sintered magnet, bonded permanent magnet, magnetic recording medium etc., can make it to have given play to high-performance.During particularly as the main composition thing of ferrite sintered magnet, can obtain maintaining high B rwith high H k/ H cJstate under make H cJthe ferrite sintered magnet improving, can tackle slimming, this ferrite sintered magnet can be applicable to being used in automobile electrical dress part, the electric installation part etc. of various electric motor, generator, loud speaker etc., particularly can contribute to small-sized, lightweight, the high efficiency of these parts.

Claims (3)

1. a ferrite compounds, is characterized in that, is to have the M type magnetoplumbite type of hexagonal crystal and contain Ca, La, Fe and the Co ferrite compounds as essential component, wherein, is present in 2a, 4e, 4f in the unit cell of described M type magnetoplumbite type 1, 4f 2with in the total amount per unit structure cell of the Ca of the brilliant position of 12k, be more than 0.05.
2. ferrite compounds according to claim 1, is characterized in that, is representing Ca, La, composition formula as the atom ratio of the metallic element of A element, Fe and the Co of Ba and/or Sr: Ca 1-x-yla xa yfe 2n-z-wco zca win, the n of described 1-x-y, x, y, z, w and expression mol ratio meets:
0.23≤(1-x-y+w)/(1+w)≤0.75、
0.2≤x/(1+w)≤0.65、
0≤y/(1+w)≤0.4、
0.2≤z/(1+w)＜0.65、
w≥0.025、
3 < n/ (1+w) < 6 and
0≤y/(1-x+w)＜0.56。
3. ferrite compounds according to claim 1 and 2, it is characterized in that, described ferrite compounds is manufactured and is formed in the following way: pulverize raw material powder is carried out to the pre-burning body that pre-burning forms, taking the heat-up rate of the temperature range of 1100 DEG C～firing temperature as 1～4 DEG C/min, and the cooling rate of the temperature range of firing temperature～1100 DEG C is that 6 DEG C/min of above conditions are burnt till.
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