CN100573748C - Ferrite sintered magnet - Google Patents
Ferrite sintered magnet Download PDFInfo
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- CN100573748C CN100573748C CNB200510118623XA CN200510118623A CN100573748C CN 100573748 C CN100573748 C CN 100573748C CN B200510118623X A CNB200510118623X A CN B200510118623XA CN 200510118623 A CN200510118623 A CN 200510118623A CN 100573748 C CN100573748 C CN 100573748C
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Abstract
The purpose of this invention is to provide a kind ofly under the situation of the content that does not increase Co, can improve the remanence Br of the M type ferrite sintered magnet that contains La-Co, the technology of coercivity H J effectively.The invention provides a kind of ferrite magnetic material, it is a principal phase with the ferrite with structure of hexagonal crystal, and this principal phase contains A, La, R, Fe and Co, wherein A is at least a element of selecting among Sr, Ba and Pb, R is Pr and/or Nd, and the A in principal phase, La, R, Fe and Co metallic element total component ratio separately is not A:1～13 atom %, La:0.05～6 atom %, R:0.05～4 atom %, Fe:80～95 atom %, Co:0.05～5 atom % with the total amount score with respect to all metallic elements.Ferrite magnetic material of the present invention is by containing La and Co, contains a kind or 2 kinds among Pr and the Nd simultaneously, and under the situation of the content that does not increase Co, can improve remanence Br and coercivity H J.
Description
Technical field
The present invention relates to oxidate magnetic material, particularly relate to the M type ferrite magnet material that contains R and Co.
Background technology
As the oxide permanent magnet material, the magnetoplumbite type of general main employing hexagonal crystal system (M type) Sr ferrite or Ba ferrite.These M type ferrite are because less expensive and have the such feature of high magnetic characteristic, so be utilized as sintered magnet or bonded permanent magnet, are applied to carry motor in for example tame electrical article or automobile etc. etc.
In recent years, the miniaturization of electronic unit, the requirement of high performance are increased, what accompany with it is that miniaturization, high performance to ferrite sintered magnet has strong requirement.For example, open in the flat 11-154604 communique (patent documentation 1) the spy and to have proposed a kind of ferrite sintered magnet, it has former M type ferrite sintered magnet inaccessiable high remanence of institute and high-coercive force.This ferrite sintered magnet contains Sr, La and Co at least, and has the main component of hexagonal crystal M type ferrite.And, open flat 11-97226 communique (patent documentation 2) the spy, the spy opens and discloses the relevant Sr of having, Pr and Co in the flat 11-195516 communique (patent documentation 3) or had the hexagonal crystal M type ferrite of Sr, Nd and Co.
But, in these ferrimagnets, also further require to improve the improvement of confining force and this two specific character of saturation magnetization.And, contain Co by making these ferrimagnets, thereby coercive force (HcJ) and remanence (Br) are improved, but because Co price height causes the cost of ferrimagnet to raise.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind ofly under the situation of the content that does not increase Co, can improve the remanence (Br) of ferrite sintered magnet and/or the technology of coercive force (HcJ) effectively.
Present inventors study the magnetic characteristic raising of hexagonal crystal M type ferrite sintered magnet, found that, in the ferrite that obtains with the part of the main component of La and Co displacement hexagonal crystal M type ferrite, a kind or 2 kinds that contains among Pr and the Nd is effective.That is to say, the invention provides a kind of ferrite magnetic material, it is a principal phase with the ferrite with structure of hexagonal crystal, and described principal phase contains A, La, R, Fe and Co, wherein A is from Sr, at least a element of selecting among Ba and the Pb, R is Pr and/or Nd, the A in the described principal phase, La, R, Fe and Co metallic element total component ratio separately with the total amount score with respect to all metallic elements is not: A:1～13 atom %, La:0.003～10 atom %, R:0～10 atom % (not comprising 0), Fe:80～95 atom %, Co:0.05～5 atom %.
Under the situation of M type ferrite displacement La and Co, except La, a kind or 2 kinds that also further contains among Pr and the Nd is effectively, wherein preferably with composition formula: A
1-x(La
1-mR
m)
x(Fe
12-yCo
y)
zO
19The composition of expression is a main component, and wherein, A is that at least a, the R that select among Sr, Ba and Pb are 1 kinds or 2 kinds among Pr and the Nd, 0.04≤x＜0.80,0.02≤y＜0.40,0.0＜m＜0.9 and 0.9＜z＜1.1.
And, among the present invention, in the aforementioned component formula, 1.0＜x/yz＜2.5 preferably.Like this magnetic characteristic raising effect becomes remarkable.
In addition, in the present invention, with respect to aforementioned main component to be converted into SiO
2Meter contains the Si composition of 0.15～1.35wt%, and can contain the Ca composition, and wherein the ratio Ca/Si of the mole of the mole of Ca composition and Si composition is 0.35～2.10 scope.
Ferrite magnetic material of the present invention can be used as ferrite sintered magnet and is used.This ferrite sintered magnet can obtain by carrying out sintering after the processing that material powder is implemented to be scheduled to.And ferrite magnetic material of the present invention can be used with the form of ferrimagnet particle.The ferrimagnet particle typically is used as the magnetic particle of bonded permanent magnet.In addition, ferrite magnetic material of the present invention can also be as the magnetic film of magnetic recording media and is used.The form of these utilizations is typical examples, also goes for the purposes outside above-mentioned these purposes of ferrite magnetic material of the present invention.
In addition, ferrite magnetic material of the present invention can contain the Si composition as accessory ingredient.As the Si composition, can list SiO
2Interpolation period of Si composition is preferably before the pre-burning operation, more particularly preferably when compounding operation.By a part with Pr and/or Nd displacement La, simultaneously the total amount of adding the Si composition before the pre-burning operation 40% or more than, can seek the raising of magnetic characteristic.
According to the present invention,, can improve the magnetic characteristic of ferrite magnetic material by a part with Pr and/or Nd displacement La.Specifically, can have 4000Oe or above coercive force (HcJ) and 4000G or above remanence (Br) concurrently.In addition, also can have 4500Oe or above coercive force (HcJ) and 4200G or above remanence (Br) concurrently.
And, owing to can improve magnetic characteristic,, also can obtain high characteristic even reduce the content of the high Co of price.
Description of drawings
Fig. 1 be expression among the embodiment 1 m and the tables of data of the relation between the magnetic characteristic.
Fig. 2 be expression among the embodiment 1 m and the chart of the relation between the coercive force (HcJ).
Fig. 3 be expression among the embodiment 1 m and the chart of the relation between the remanence (Br).
Fig. 4 be expression among the embodiment 1 m and the chart of the relation between the square property (Hk/HcJ).
Fig. 5 be expression among the embodiment 2 x/yz and the tables of data of the relation between the magnetic characteristic.
Fig. 6 be expression among the embodiment 2 x/yz and the chart of the relation between the coercive force (HcJ).
Fig. 7 be expression among the embodiment 2 x/yz and the chart of the relation between the remanence (Br).
Fig. 8 is the x among the expression embodiment 3, y, the tables of data of the relation between m and the magnetic characteristic.
Fig. 9 be expression among the embodiment 4 z and the tables of data of the relation between the magnetic characteristic.
Figure 10 be expression among the embodiment 4 z and the chart of the relation between the coercive force (HcJ).
Figure 11 be expression among the embodiment 4 z and the chart of the relation between the remanence (Br).
Figure 12 be expression among the embodiment 5 x/yz and the tables of data of the relation between mx and the magnetic characteristic.
Figure 13 be expression among the embodiment 5 m and the chart of the relation between the coercive force (HcJ).
Figure 14 be expression among the embodiment 5 m and the chart of the relation between the remanence (Br).
Figure 15 is among the expression embodiment 6, the tables of data of the magnetic characteristic when using Ba as the A element.
Figure 16 is the tables of data of the temperature coefficient of the expression coercive force (HcJ) of trying to achieve among the embodiment 7.
Figure 17 is the chart of the relation between the temperature characterisitic of expression Pr replacement amount and coercive force (HcJ).
Figure 18 is that expression has or not the tables of data that contains the relation between Pr and the crystallization magnetic anisotropy K1.
Figure 19 is 1/H and the crystallization magnetic anisotropy K among the expression embodiment 8
1Between the chart of relation.
Figure 20 is the SiO among the expression embodiment 9
2The tables of data of the relation between addition and the magnetic characteristic.
Figure 21 is illustrated under the situation of Ca/Si=0.70 SiO
2The chart of the relation between addition and the coercive force (HcJ).
Figure 22 is illustrated under the situation of Ca/Si=0.70 SiO
2The chart of the relation between addition and the remanence (Br).
Figure 23 is illustrated under the situation of Ca/Si=1.40 SiO
2The chart of the relation between addition and the coercive force (HcJ).
Figure 24 is illustrated under the situation of Ca/Si=1.40 SiO
2The chart of the relation between addition and the remanence (Br).
Figure 25 is illustrated under the situation of Ca/Si=1.75 SiO
2The chart of the relation between addition and the coercive force (HcJ).
Figure 26 is illustrated under the situation of Ca/Si=1.75 SiO
2The chart of the relation between addition and the remanence (Br).
Figure 27 be expression among the embodiment 10 Ca/Si and the tables of data of the relation between the magnetic characteristic.
Figure 28 is illustrated in SiO
2Under the situation of addition=0.30wt%, the chart of the relation between Ca/Si and the coercive force (HcJ).
Figure 29 is illustrated in SiO
2Under the situation of addition=0.30wt%, the chart of the relation between Ca/Si and the remanence (Br).
Figure 30 is illustrated in SiO
2Under the situation of addition=0.60wt%, the chart of the relation between Ca/Si and the coercive force (HcJ).
Figure 31 is illustrated in SiO
2Under the situation of addition=0.60wt%, the chart of the relation between Ca/Si and the remanence (Br).
Figure 32 is illustrated in SiO
2Under the situation of addition=0.90wt%, the chart of the relation between Ca/Si and the coercive force (HcJ).
Figure 33 is illustrated in SiO
2Under the situation of addition=0.90wt%, the chart of the relation between Ca/Si and the remanence (Br).
Figure 34 be added before being illustrated under the situation of Pr and La magnetic characteristic and after added the tables of data of the magnetic characteristic under the situation of Pr and La.
Figure 35 be added before being illustrated under the situation of Pr and La magnetic characteristic and after added the chart of the magnetic characteristic under the situation of Pr and La.
Figure 36 is that the tables of data of Nd as the magnetic characteristic under the situation of R element added in expression.
Figure 37 be expression among the embodiment 12 m and the chart of the relation between the coercive force (HcJ).
Figure 38 be expression among the embodiment 12 m and the chart of the relation between the remanence (Br).
Figure 39 is the tables of data of the assay value (atom %) of the sintered body of making among the expression embodiment 1.
Figure 40 is the tables of data of the assay value (atom %) of the sintered body of making among the expression embodiment 2.
Figure 41 is the tables of data of the assay value (atom %) of the sintered body of making among the expression embodiment 4.
Figure 42 is the tables of data of the assay value (atom %) of the sintered body of making among the expression embodiment 12.
Figure 43 is the Si composition (SiO among the expression embodiment 13
2) interpolation period and the tables of data of the relation between the magnetic characteristic.
Figure 44 is expression SiO
2The ratio of preceding addition and the chart of the relation between the remanence (Br).
Figure 45 is expression SiO
2The ratio of preceding addition and the chart of the relation between the coercive force (HcJ).
Embodiment
Below explain ferrite magnetic material of the present invention.
Ferrite magnetic material of the present invention is to be principal phase with the ferrite with structure of hexagonal crystal, and A, La, R, Fe and Co metallic element total component ratio separately with the total amount score with respect to all metallic elements is not in this principal phase:
A:1～13 atom %,
La:0.003～10 atom %,
R:0～10 atom % (but not comprising 0),
Fe:80～95 atom %,
Co:0.05～5 atom %.
Wherein, A is that at least a element, the R that selects among Sr, Ba and Pb is Pr and/or Nd.
If A is too small, then do not generate M type ferrite, perhaps α-Fe
2O
3Increase mutually etc. non magnetic.If A is excessive, then do not generate M type ferrite, perhaps SrFeO
3-xIncrease mutually etc. non magnetic.Therefore, the A that contains 1～13 atom % among the present invention.The preferable range of A is 3～11 atom %, further 3～9 atom % preferably.
The ratio of Sr among the A preferably 50 atom % or above, be more preferably 70 atom % or above, further 100 atom % preferably.If the ratio of the Sr among the A is low excessively, can not realize together that then saturation magnetization improves and coercitive significantly improving.
For R, R is a kind or 2 kinds among Pr and the Nd, wherein is that must composition to improve for magnetic characteristic be preferred with Pr.
When R surpassed 0, magnetic characteristic improved, but when R surpasses 10 atom %, as square property (Hk/HcJ) variation of one of index of magnetic characteristic, was difficult to obtain the magnet of practicality.Therefore, in the present invention, contain 0～10 atom % R of (but not comprising 0).The preferable range of R is 0.005～5.4 atom %, further 0.01～3.6 atom % preferably.
If the La amount is very few, can not guarantee predetermined solid solution capacity with respect to the Co of hexagonal crystal M type ferrite, saturation magnetization improves effect and/or anisotropy field raising effect is insufficient.On the contrary, if the La amount is excessive, owing to there is the La of the surplus that can not replace solid solution in the hexagonal crystal M type ferrite, generate the out-phase such as orthoferrite that for example contain element R thus, so magnetic characteristic reduces.
Therefore, in the present invention, contain the La of 0.003～10 atom %.The preferable range of La is 0.05～6.0 atom %, further 0.5～4.0 atom % preferably.
If the Co amount is very few, then saturation magnetization raising effect and/or anisotropy field raising effect are insufficient.But,, then in hexagonal crystal M type ferrite, have the Co of the surplus that can not replace solid solution if the Co amount is excessive.Therefore, in the present invention, contain the Co of 0.05～5 atom %.The preferable range of Co is 0.1～4.0 atom %, further 0.15～3.0 atom % preferably.
If the Fe amount is very few, then do not generate M type ferrite, perhaps SrFeO
3-xIncrease mutually etc. non magnetic.But,, then do not generate M type ferrite, perhaps α-Fe if the Fe amount is too much
2O
3Increase mutually etc. non magnetic.Therefore, the Fe that contains 80～95 atom % in the present invention.The preferable range of Fe is 83～94 atom %, further 86～93 atom % preferably.
And ferrite magnetic material of the present invention is especially preferably with composition formula: A
1-x(La
1 -mR
m)
x(Fe
12-yCo
y)
zO
19The composition of expression is a main component, and wherein A is select among Sr, Ba and Pb at least a, and R is a kind or 2 kinds among Pr and the Nd, 0.04≤x＜0.80,0.02≤y＜0.40,0.00＜m＜0.90 and 0.90＜z＜1.10.
Qualification reason to above-mentioned composition formula describes below.
(La
1-mR
m)(x)：
In the above-mentioned formula (1), if x is too small, just if (La
1-mR
m) amount very few, then can not guarantee predetermined solid solution capacity, and saturation magnetization improves effect and/or anisotropy field, and to improve effect insufficient with respect to the Co of hexagonal crystal M type ferrite.Conversely, if x is excessive, owing to there is (the La of the surplus that can not replace solid solution in the hexagonal crystal M type ferrite
1-mR
m), generate the out-phase such as orthoferrite that for example contain element R thus, so magnetic characteristic reduces.So the present invention sets 0.04≤x＜0.80.The value of x is 0.04≤x≤0.45 preferably, is more preferably 0.05≤x≤0.30, further 0.05≤x≤0.25 preferably.R(m)：
Wherein, R is a kind or 2 kinds among Pr and the Nd, wherein is composition to be preferred for improving magnetic characteristic with Pr.
When m surpassed 0, magnetic characteristic improved, but reached 0.90 or when above as m, as square property (Hk/HcJ) variation of one of index of magnetic characteristic, was difficult to obtain the magnet of practicality.Therefore, the present invention sets 0.0＜m＜0.9.The value of m is 0.01≤m≤0.70 preferably, and the value of m is more preferably 0.04≤m≤0.60.
A：
A is at least a element of selecting among Sr, Ba and Pb.From improving the viewpoint of coercive force (HcJ), most preferably use Sr among the A.
Co(y)：
If the y of expression Co amount is too small, saturation magnetization improves effect and/or anisotropy field raising effect is insufficient.But,, then in hexagonal crystal M type ferrite, have the Co of the surplus that can not replace solid solution if y is excessive.And even in Co can replace the scope of solid solution, the variation of anisotropy constant (K1) or anisotropy field (Ha) also strengthens.Therefore, the present invention sets 0.02≤y＜0.40.The value of y is 0.02≤y≤0.30 preferably, and further 0.04≤y≤0.20 preferably is more preferably 0.06≤y≤0.20.
z：
At composition formula A
1-x(La
1-mR
m)
x(Fe
12-yCo
y)
zO
19In, if z is too small, the out-phase that then contains Sr or element R increases, and when if z is excessive, then contains α-Fe
2O
3Or the equal out-phase increase of the ferrospinel of element M, so magnetic characteristic reduces.Therefore, the z among the present invention is preferably set to 0.90＜z＜1.10.The value of z is 0.96≤z≤1.05 preferably, and the value of z is more preferably 0.97≤z≤1.04.
x/yz：
For ferrite magnetic material of the present invention, preferably, the x/yz of the total amount of expression La and R and the ratio of Co amount is set at 1.0＜x/yz＜2.5.In the past, as disclosed in aforesaid patent documentation 1～3, this ratio it is desirable to 1.But, as embodiment described later obviously show like that, if x/yz surpasses 1.1, then magnetic characteristic improves, so more preferably x/yz is set at 1.1≤x/yz≤2.3, more preferably is set at 1.3≤x/yz≤2.0.
In composition formula of the present invention, the atomicity of oxygen O is 19, and this has shown that Co all is a divalent, and La and R all are 3 valencys, and the stoichiometric composition ratio of the oxygen when x=y, z=1.Along with the difference of the value of x, y, z, the atomicity of oxygen also is different.For example when burning till gas medium and be the reducibility gas medium, the possibility of damaged (the ベ イ カ Application シ one) that produce oxygen is arranged.In addition, Fe exists with 3 valencys in the M type ferrite usually, but this also may be varied to divalent etc.And the variation of valence mumber also might take place in Co, and also may adopt the valence mumber beyond 3 valencys for La and R, and the ratio with respect to the oxygen of metallic element changes thus.In this manual, the atomicity of oxygen is expressed as 19, and does not change, but the atomicity of actual oxygen can be the value of bias more or less therewith along with the variation of the value of x, y, z.
The composition of ferrite magnetic material of the present invention can not contain main component and accessory ingredient composition in addition but do not get rid of by mensuration such as fluorescent X-ray quantitative analyses.And the existence of above-mentioned principal phase can be confirmed by X-ray diffraction or electronics line diffraction etc.
In ferrite magnetic material of the present invention,, can contain Si composition and Ca composition as accessory ingredient.The purpose of adding Si composition and Ca composition is to improve the agglutinating property of hexagonal crystal M type ferrite, control magnetic characteristic and adjust crystallization particle diameter of sintered body or the like.
As Si composition and Ca composition, preferably use SiO separately
2And CaCO
3, but be not limited to this example, can use the compound that can realize effect of the present invention aptly.The addition of Si composition is to be converted into SiO
2Meter is 0.15～1.35wt% preferably, and the ratio Ca/Si of the mole of the mole of Ca composition and Si composition is 0.35～2.10, more preferably to be converted into SiO
2Counting 0.30～0.90wt%, Ca/Si is 0.70～1.75, and further preferably 0.45～0.90wt%, Ca/Si are 1.05～1.75.
In ferrite magnetic material of the present invention,, also can contain Al as accessory ingredient
2O
3And/or Cr
2O
3Al
2O
3And Cr
2O
3Coercive force is improved, but remanence is reduced.In order to suppress the reduction of remanence, Al
2O
3And Cr
2O
3Total content 3 quality % or following preferably.And add Al in order to bring into play fully
2O
3And/or Cr
2O
3Effect, Al
2O
3And Cr
2O
3Total content preferably 0.1 quality % or more than.
In ferrite magnetic material of the present invention,, also can contain B as accessory ingredient
2O
3By containing B
2O
3, can reduce calcined temperature and sintering temperature, so on producing, be favourable.B
2O
3The content 0.5wt% of whole ferrite magnetic material or following preferably.If B
2O
3Content is too much, and then saturation magnetization reduces.
In ferrite magnetic material of the present invention, preferably do not contain alkali metals such as Na, K, Rb, but can contain with the form of impurity.When they are converted into Na
2O, K
2O, Rb
2Oxides such as O and when asking for content, the summation of their content is 3 quality % or following of whole ferrite cemented body preferably.If their content is too much, then saturation magnetization reduces.
And, except above-mentioned, also can contain for example Ga, Mg, Cu, Mn, Ni, Zn, In, Li, Ti, Zr, Ge, Sn, V, Nb, Ta, Sb, As, W, Mo etc. with the form of oxide.Their content is scored not preferably with the oxide that is converted into stoichiometric composition: gallium oxide: 5wt% or following, magnesium oxide: 5wt% or following, cupric oxide: 5wt% or following, manganese oxide: 5wt% or following, nickel oxide: 5wt% or following, zinc oxide: 5wt% or following, indium oxide: 3wt% or following, lithia: 1wt% or following, titanium oxide: 3wt% or following, zirconia: 3wt% or following, germanium oxide: 3wt% or following, tin oxide: 3wt% or following, vanadium oxide: 3wt% or following, niobium oxide: 3wt% or following, tantalum oxide: 3wt% or following, antimony oxide: 3wt% or following, arsenic oxide arsenoxide: 3wt% or following, tungsten oxide: 3wt% or following, and molybdenum oxide: 3wt% or following.
Become the occasion of the form of ferrite cemented body at ferrite magnetic material of the present invention, its average crystallite particle diameter preferably 1.5 μ m or following, be more preferably 1.0 μ m or following, further 0.5～1.0 μ m preferably.The crystallization particle diameter can be measured by scanning electron microscope.
And ferrite magnetic material of the present invention becomes the occasion of the form of ferrite particle, even the average grain diameter of its 1 particle surpasses 1 μ m, also can obtain than high in the past coercive force.The average grain diameter of 1 particle preferably 2 μ m or following, be more preferably 1 μ m or following, further 0.1～1 μ m preferably.If average grain diameter is excessive, then the ratio of the many magnetic domains particle in the ferrite particle increases, and coercive force reduces, and if average grain diameter is too small, then because the heat upset reduces magnetic, and perhaps directionality or the mouldability variation during moulding in the magnetic field.
Ferrite particle be generally used for by adhesive with its in conjunction with and the bonded permanent magnet that obtains.As adhesive, can use acrylonitrile-butadiene rubber (NBR rubber), haloflex, nylon 12 (polyamide), nylon 6 (polyamide) usually.
Next the preferred manufacture method to ferrite magnetic material of the present invention is described.
At first the manufacture method to ferrite particle describes.
As the manufacture method of ferrite particle, can use liquid phase method, separating out of glass method, spray heating decompositions such as solid reaction process, co-electrodeposition method or hydrothermal synthesis method, the whole bag of tricks such as vapor phase method.Wherein, the manufacture method of the ferrite particle of using as bonded permanent magnet, at present in industry the most extensive employing be solid reaction process.
For solid reaction process, the powder that contains Fe, elements A, La, element R, Co and Si, Ca by use is as raw material, and the mixture of these powder is burnt till (pre-burning), makes ferrite particle thus.In this pre-burning body, ferritic primary particle condenses, and becomes so-called " particle " state.Therefore, to pulverize as a rule thereafter.Pulverizing is to carry out with dry type or wet type, but makes magnetic characteristic (mainly being coercive force) variation owing to introduced strain in this case in ferrite particle, so will carry out annealing in process as a rule after pulverizing.
Pre-burning can be for example to carry out under 1000～1350 ℃ 1 second～10 hours in air, about particularly 1 second～3 hours.The pre-burning body that obtains like this has the ferrite structure of magnetoplumbite type in fact, the average grain diameter of its primary particle preferably 2 μ m or following, be more preferably 1 μ m or following, further preferably 0.1～1 μ m, most preferably be 0.1～0.5 μ m.Average grain diameter can be measured by scanning electron microscope.
Usually the pre-burning body is pulverized then or broken and make the powder of ferrite particle.And, under the situation of utilizing this ferrite particle as bonded permanent magnet that various adhesives such as itself and resin, metal, rubber are mixing, moulding or not moulding in magnetic field in magnetic field.Afterwards, harden as required and make bonded permanent magnet.
Next ferrite cemented body is described.
By making ferrite cemented body with the ferrite particle moulding and the sintering of the whole bag of tricks manufacturing described in the manufacture method of above-mentioned ferrite particle.
The pre-burning body that the material powder pre-burning is made generally is granular, for its pulverizing or fragmentation, at first preferably carries out the dry type coarse crushing.Impurity that is contained in raw material and the Si that is added or Ca are segregated in most of crystal boundary or triple point (or being called triple point) part, and a part enters in the ferrite part (principal phase) of intragranular.It is big that the spy is that Ca enters the possibility that Sr orders.
After the dry type coarse crushing, preferably, the pulverizing slurry that preparation contains ferrite particle and water uses this slurry to carry out case of wet attrition.
After the case of wet attrition, will pulverize with slurry and concentrate and preparation moulding slurry.Concentrate and to be undertaken by centrifugation or filter press etc.
Moulding can be carried out with dry type, also can carry out with wet type, but in order to improve degree of orientation, preferably carries out the wet type moulding.
For the wet type molding procedure, be to use moulding to carry out moulding with slurry and in magnetic field.Briquetting pressure is 0.1～0.5 ton/cm
2About, externally-applied magnetic field is to get final product about 5～15kOe.
After the wet type molding procedure, formed body is heat-treated with 100～500 ℃ temperature in atmosphere or in the nitrogen, decompose fully and remove with the dispersant that will add.Then in sintering circuit, with formed body for example in atmosphere preferably 1150～1270 ℃, be more preferably 1160～1240 ℃ temperature sintering about 0.5～3 hour, obtain the anisotropic ferrite sintered body.
In above manufacture method, there is no particular limitation period to the interpolation of La and/or R, adds get final product preferably interpolation when raw material mixes as required in suitable period.In addition, in the present invention, the interpolation of carrying out when raw material is cooperated is defined as preceding interpolation, add and the interpolation of carrying out when the pulverizing of pre-burning powder is defined as the back, below like this too.
And also there is no particular limitation period for the interpolation of Co, adds get final product as required in suitable period, but preferably back interpolation.
Also there is no particular limitation period to the interpolation of Si, adds get final product as required in suitable period, but preferably 40% of the interpolation total amount or more than.Before preferred addition be total amount 50% or above, further preferably 80% of total amount or more than, add whole total amount before more preferably.
And also there is no particular limitation period to the interpolation of Ca, adds get final product as required in suitable period, preferred back add total amount 50% or more than, the more preferably whole total amount of back interpolation.
Secondly, for the formation of thin film magnetic layer, preferably utilize sputtering method usually.In the occasion of using sputtering method, can also can utilize the polynary sputtering method of at least 2 kinds of oxide targets of employing with above-mentioned sintered magnet as target.After sputtered film forms,, also implement heat treatment sometimes in order to form hexagonal crystal magnetoplumbite structure.
Preparation iron oxide (Fe
2O
3), strontium carbonate (SrCO
3), praseodymium oxide (Pr
6O
11) and lanthanum hydroxide (La (OH)
3) as initiation material.These initiation materials that constitute main component are carried out weighing so that the main component after burning till is following composition formula, add silica (SiO then
2) so that it is 0.6wt% with respect to main component.
Composition formula: A
1-x(La
1-mR
m)
x(Fe
12-yCo
y)
zO
19
A=Sr wherein, R=Pr
x＝0.12，y＝0.08，z＝1.00
m＝0～1.0
x/yz＝1.5
This mixed material is mixed with wet grinding machine and pulverized 2 hours.Carried out pre-burning 2.5 hours after the mixed slurry drying with gained, in atmosphere.Calcined temperature is set at 1100 ℃ or 1150 ℃.
With the pre-burning powder of gained with small-sized bar vibration milling coarse crushing 10 minutes.Weighing is also added cobalt oxide (Co
3O
4) so that become main composition after aforesaid the burning till, add calcium carbonate (CaCO then with respect to the meal flour of gained
3) and D-sorbite so that form calcium carbonate (CaCO with respect to main after aforesaid the burning till
3) for 1.4wt% and D-sorbite are 0.9wt%, and with the wet ball-milling micro mist broken 25 hours.
The solid formation branch concentration of the micro mist pulping material of gained is adjusted to 70～75%, uses wet type pressing under magnetic field machine, in the externally-applied magnetic field of 12kOe, obtain the cylindric formed body of diameter 30mm * thickness 15mm.Formed body is intensive drying in atmosphere, under room temperature, then burns till in atmosphere 1 hour.Firing temperature is set at 1180 ℃ or 1200 ℃.
After the top and bottom of prepared cylindric sintered body are processed, use the B-H plotter of maximum externally-applied magnetic field, measure coercive force (HcJ), remanence (Br) and square property (Hk/HcJ) as 25kOe.And Hk is in the 2nd quadrant of magnetic hysteresis loop, and magnetic flux density is 90% o'clock an external magnetic field Strong degree of remanence.It the results are shown among Fig. 1～Fig. 4.
As Fig. 2 and shown in Figure 3, if pre-burning and the condition variation of burning till, then remanence of gained (Br) and coercive force (HcJ) also change, but in any of Fig. 2 and four kinds of situations shown in Figure 3, remanence (Br) and coercive force (HcJ) are improved.But, as shown in Figure 4, if m be 0.9 or more than, then square property (Hk/HcJ) is reduced near 80%.If the square property (Hk/HcJ) in the demagnetizing curve reduces, then have (BH) max to reduce, simultaneously through the time change problem such as increase, can not be as the magnet of practicality.Thereby, set 0.0＜m＜0.9.
In order to suppress the reduction of square property (Hk/HcJ), and obtain high remanence (Br) and coercive force (HcJ), can confirm preferably 0.01≤m≤0.70,0.04≤m≤0.60 more preferably.
Embodiment 2
In embodiment 2, confirmed the preferable range of x/yz.
So that the master after burning till consists of the following composition formula, make cylindric sintered body except initiation material is carried out weighing, measure coercive force (HcJ) and remanence (Br) similarly to Example 1 according to condition similarly to Example 1.It the results are shown among Fig. 5～Fig. 7.
Composition formula: A
1-x(La
1-mR
m)
x(Fe
12-yCo
y)
zO
19
A=Sr wherein, R=Pr
y＝0.08，z＝1.00
m＝0、0.33
For m=0.33, mx=0.04
x/yz＝0.8～2.5
As shown in Figure 6 and Figure 7, in the scope of 1.0＜x/yz＜2.5, by containing Pr, the occasion that has obtained than m=0, promptly not containing Pr has higher coercive force (HcJ) and remanence (Br).In the occasion of paying attention to coercive force (HcJ), the scope of preferred 1.1≤x/yz≤2.3, further 1.2≤x/yz≤1.8 preferably.And in the occasion of paying attention to remanence (Br), the scope of 1.0＜x/yz≤1.4 and 1.9≤x/yz＜2.5 is preferred.
In embodiment 3, confirmed x, y, the relation between m and the magnetic characteristic.
So that the master after burning till consists of the following composition formula, make cylindric sintered body except initiation material is carried out weighing, measure coercive force (HcJ) and remanence (Br) similarly to Example 1 according to condition similarly to Example 1.It the results are shown among Fig. 8.
Composition formula: A
1-x(La
1-mR
m)
x(Fe
12-yCo
y)
zO
19
A=Sr wherein, R=Pr
x＝0.04～0.80，y＝0.02～0.40
z＝1.00，m＝0.00～0.33
As shown in Figure 8, when x=0.80 or y=0.40, then cause the effect of magnetic characteristic raising saturated owing to containing Pr.Thus, with x, the upper limit of y is set at x＜0.8, y＜0.4 respectively.
For x, preferably 0.04≤x≤0.45,0.05≤x≤0.30 more preferably.For y, preferably 0.02≤y≤0.30,0.05≤y≤0.20 more preferably.
In the occasion of y=0.02, y=0.08, promptly the amount of Co after a little while, then to improve effect be significant owing to containing magnetic characteristic that Pr causes.
Embodiment 4
In embodiment 4, confirmed the preferable range of z.
So that the master after burning till consists of the following composition formula, make cylindric sintered body except initiation material is carried out weighing, measure coercive force (HcJ) and remanence (Br) similarly to Example 1 according to condition similarly to Example 1.It the results are shown among Fig. 9～Figure 11.In addition, calcined temperature is set at 1150 ℃, and firing temperature is set at 1200 ℃.
Composition formula: A
1-x(La
1-mR
m)
x(Fe
12-yCo
y)
zO
19
A=Sr wherein, R=Pr
x＝0.12，z＝0.90～1.10
yz＝0.08
m＝0、0.33
As shown in figure 10, in the scope of 0.90＜z＜1.10,, compare with the situation that does not contain Pr and can obtain higher coercive force (HcJ) by containing Pr.
Moreover, as shown in Figure 9, when m=0.33, in the scope of 0.92≤z≤1.05, can obtain 4000Oe or above coercive force (HcJ) and 4270G or above remanence (Br), in the scope of 0.95≤z≤1.04, can obtain 4200Oe or above coercive force (HcJ) and 4270G or above remanence (Br).
Embodiment 5
In embodiment 5, confirmed the variation of the magnetic characteristic when making x/yz and mx change.
Employed initiation material weighing among the embodiment 1 so that being following composition formula, the main component after burning till is added silica (SiO then
2) so that it is 0.6wt% with respect to main component.This mixed material is mixed with wet grinding machine and pulverized 2 hours.After the mixed slurry drying with gained, in atmosphere, under 1150 ℃, carry out pre-burning 2 hours.
With the pre-burning powder of gained with small-sized bar vibration milling coarse crushing 17 minutes.Weighing is also added cobalt oxide (Co
3O
4) so that become main composition after aforesaid the burning till, add calcium carbonate (CaCO then with respect to the meal flour of gained
3) and D-sorbite so that form calcium carbonate (CaCO with respect to main after aforesaid the burning till
3) be 1.4wt%, and D-sorbite is 0.5wt%, and carried out micro mist broken 2 hours with wet grinding machine.
Composition formula: A
1-x(La
1-mR
m)
x(Fe
12-yCo
y)
zO
19
A=Sr wherein, R=Pr
mx＝0～0.05，z＝1.00
y＝0.08
Ca/Si＝1.4
Except above-mentioned aspect, make cylindric sintered body according to condition similarly to Example 1, measure coercive force (HcJ) and remanence (Br) similarly to Example 1.It the results are shown among Figure 12～Figure 14.
As Figure 13 and shown in Figure 14,, still can confirm owing to containing the effect that magnetic characteristic that Pr causes improves even the value of x/yz changes in the scope that the present invention recommended.
Embodiment 6
The having or not of effect of containing Pr when in embodiment 6, having confirmed to use Ba as the A element.
As the initiation material that constitutes main component, further prepare brium carbonate (BaCO
3), and initiation material carried out weighing so that the master after burning till consists of following composition formula, and in addition, make cylindric sintered body according to condition similarly to Example 1, measure coercive force (HcJ) and remanence (Br) similarly to Example 1.It the results are shown among Figure 15.
Composition formula: A
1-x(La
1-mR
m)
x(Fe
12-yCo
y)
zO
19
A＝Sr，Ba
R＝Pr
x＝0.12，y＝0.08，z＝1.00
m＝0，0.33
As shown in figure 15, in the occasion of using Ba as the A element, also can confirm by containing the effect that magnetic characteristic that Pr causes improves.And can confirm that compare with the sintered body of the Ba of the Sr that contains 50 atom %, 50 atom %, the sintered body that contains 100% Sr shows higher magnetic characteristic.
Embodiment 7
In embodiment 7, confirmed the relation between the temperature characterisitic of m and coercive force (HcJ).
Except being carried out weighing, initiation material, makes cylindric sintered body according to condition similarly to Example 1 so that the master after burning till consists of the following composition formula.And, calcined temperature is set at 1100 ℃, firing temperature is set at 1180 ℃.
Composition formula: A
1-x(La
1-mR
m)
x(Fe
12-yCo
y)
zO
19
A=Sr wherein, R=Pr
x＝0.12，y＝0.08，z＝1.00
m＝0，0.08，0.33
For the sintered body of gained, ask for I-H B-H loop from-80 ℃ to 160 ℃ temperature range by vibration sample type magnetometer (VSM, VibratingSample Magnetometer).By this I-H B-H loop, the temperature dependency of investigation coercive force (HcJ).Use this result, at the temperature coefficient of in-40 ℃ to 120 ℃ scope, calculating coercive force (HcJ) by straight-line approximation method.It is the results are shown among Figure 16.And, the relation between the temperature characterisitic of Pr replacement amount and coercive force (HcJ) is shown among Figure 17.
In addition, temperature coefficient Δ HcJ/HcJ/ Δ T is the rate of change with respect to the coercive force (HcJ) under 20 ℃.That is to say, the Δ T among Figure 16, Δ HcJ/HcJ is as shown below.
ΔT＝120℃-(-40℃)＝160℃
Coercive force under Δ HcJ/HcJ={120 ℃-(coercive forces under 40 ℃) }/coercive force under 20 ℃
As shown in figure 17, can confirm that the temperature characterisitic of coercive force (HcJ) is improved along with the Pr replacement amount increases.
Embodiment 8
In embodiment 8, m and crystallization magnetic anisotropy constant K have been confirmed
1Between relation.Wherein, the same remanence of coercive force (HcJ) (Br) all is important magnet characteristics together, coercive force (HcJ) and anisotropy field (HA (=2K
1/ Is)) and the long-pending (HA * fc) proportional of single magnetic domain particle ratio (fc).Crystallization magnetic anisotropy constant K
1Be the constant that crystalline texture determined by magnet, and the value of left and right sides coercive force (HcJ).If can increase crystallization magnetic anisotropy constant K
1, be favourable then for obtaining high coercive force (HcJ).
Except being carried out weighing, initiation material, makes cylindric sintered body according to condition similarly to Example 1 so that the master after burning till consists of the following composition formula.In addition, calcined temperature is set at 1100 ℃, and firing temperature is set at 1180 ℃.
Composition formula: A
1-x(La
1-mR
m)
x(Fe
12-yCo
y)
zO
19
A=Sr wherein, R=Pr
x＝0.12，y＝0.08，z＝1.00
m＝0，0.33
For the sintered body of gained, try to achieve crystallization magnetic anisotropy K by torque detection
1Torque detection is to contain the discoideus sintered body that cuts of orientation direction at the plectane face, as the torque detection sample.Then, at room temperature in applying the scope that magnetic field is H 12～20kOe, measure torque curve, then torque curve is carried out Fourier transform, try to achieve the amplitude K of 2 symmetrical compositions.The K that is tried to achieve is mapped with respect to 1/H, determine crystallization magnetic anisotropy K by being extrapolated to 1/H=0
1It the results are shown among Figure 18 and Figure 19.In addition, externally-applied magnetic field is set at 1～1.6MA/m, and temperature range is set at 80K～420K.
As Figure 18 and shown in Figure 19, improved crystallization magnetic anisotropy constant K by containing Pr
1What accompany therewith is, coercive force at room temperature (HcJ) is compared with the occasion that does not contain Pr, coercive force improve 200Oe or more than.
Embodiment 9
In embodiment 9, confirmed SiO
2Relation between addition and the magnetic characteristic.
Except with CaCO
3Addition, SiO
2Addition, Ca/Si are set at beyond the value shown in Figure 20, make cylindric sintered body according to condition similarly to Example 1, measure coercive force (HcJ) and remanence (Br) similarly to Example 1.It the results are shown among Figure 20～Figure 26.In addition, calcined temperature is set at 1100 ℃, and firing temperature is set at 1180 ℃.
As Figure 21～shown in Figure 26, when m=0, m=0.33, demonstrate same tendency.Ca/Si is in scope of recommending of the present invention, and SiO
2Addition be scope 0.15～1.35, coercive force (HcJ) and/or remanence (Br) are improved.
As Figure 21 and shown in Figure 22, when Ca/Si=0.70, SiO
2Addition is the scope 0.3～1.0, can obtain 4000Oe or above coercive force (HcJ) and 4100G or above remanence (Br).
As Figure 23 and shown in Figure 24, when Ca/Si=1.40, SiO
2Addition is in 0.2～1.2 scope, can obtain 4000Oe or above coercive force (HcJ) and 4200G or above remanence (Br).
As Figure 25 and shown in Figure 26, when Ca/Si=1.75, SiO
2Addition is in 0.2～1.0 scope, can obtain 4000Oe or above coercive force (HcJ) and 4200G or above remanence (Br).
Embodiment 10
In embodiment 10, confirmed the relation between Ca/Si and the magnetic characteristic.
Except with CaCO
3Addition, SiO
2Addition, Ca/Si are set at beyond the value shown in Figure 27, make cylindric sintered body according to condition similarly to Example 1, measure coercive force (HcJ) and remanence (Br) similarly to Example 1.It the results are shown among Figure 27～Figure 33.In addition, calcined temperature is set at 1100 ℃, and firing temperature is set at 1180 ℃.
As Figure 27～shown in Figure 33, at SiO
2Addition is under any situation of 0.30wt%, 0.60wt%, 0.90wt%, and when Ca/Si surpassed 2.10, then coercive force (HcJ) reduced greatly.And in 0.6≤Ca/Si≤1.8 o'clock, can have 4000Oe or above coercive force (HcJ) and 4000G or above remanence (Br) concurrently.
Embodiment 11
The interpolation period of R element and the relation between the magnetic characteristic in embodiment 11, have been studied.
Preparation iron oxide (Fe
2O
3), strontium carbonate (SrCO
3), praseodymium oxide (Pr
6O
11) and lanthanum hydroxide (La (OH)
3) as initiation material.At this moment, the situation of adding praseodymium oxide and lanthanum hydroxide when mixing is called preceding interpolation, adds and the situation of adding when micro mist described later is broken is called the back.
These initiation materials that constitute main component are carried out weighing so that the main component after burning till under the situation of preceding interpolation, back interpolation all reaches following composition formula, add silica (SiO then
2) make silica (SiO under the situation of preceding interpolation
2) be 0.6wt% with respect to main component.
Composition formula: A
1-x(La
1-mR
m)
x(Fe
12-yCo
y)
zO
19
A=Sr wherein, R=Pr
x＝0.12，y＝0.08，z＝1.00
m＝0，0.33
x/yz＝1.5
This mixed material is mixed with wet grinding machine and pulverized 2 hours.After the mixed slurry drying with gained, in atmosphere in 1150 ℃ of following pre-burnings 2 hours.With the pre-burning powder of gained with small-sized bar vibration milling coarse crushing 17 minutes.Weighing is also added cobalt oxide (Co
3O
4) so that become main composition after aforesaid the burning till, add calcium carbonate (CaCO then with respect to the meal flour of gained
3) and D-sorbite so that form calcium carbonate (CaCO with respect to main after aforesaid the burning till
3) be 1.4wt%, and D-sorbite is 0.5wt%.And, when mixing, do not add and under the situation of carrying out adding the back, further add main composition the after praseodymium oxide and lanthanum hydroxide make it reach aforesaid burning till, and add silica (SiO
2) so that it is 0.6wt% with respect to main component.Then, use broken 2 hours of wet grinding machine micro mist.The solid shape branch concentration of the micro mist pulping material of gained is adjusted to 70～75%, uses wet type pressing under magnetic field machine, in the externally-applied magnetic field of 12kOe, obtain the cylindric formed body of diameter 30mm * thickness 15mm.With formed body intensive drying in atmosphere, under room temperature, then in atmosphere, under 1180～1220 ℃, burnt till 1 hour.After the top and bottom processing with the cylindric sintered body of gained, use the B-H plotter of maximum externally-applied magnetic field, measure coercive force (HcJ) and remanence (Br) as 25kOe.
It is the results are shown among Figure 34 and Figure 35.Can confirm that from Figure 35 preceding interpolation Pr is effective for the aspect that obtains high remanence (Br) and high coercive force (HcJ).
Magnetic characteristic when in embodiment 12, having confirmed to use Nd as the R element.
Preparation iron oxide (Fe
2O
3), strontium carbonate (SrCO
3), neodymia (Nd
2O
3) and lanthanum hydroxide (La (OH)
3As initiation material.These initiation materials that constitute main component are carried out weighing so that the master after burning till consists of following composition formula, add silica (SiO then
2) so that it is with respect to the main 0.6wt% that consists of.
Composition formula: A
1-x(La
1-mR
m)
x(Fe
12-yCo
y)
zO
19
A=Sr wherein, R=Nd
x＝0.12，y＝0.08，z＝1.00
m＝0～0.58
In addition, make cylindric sintered body, measure coercive force (HcJ) and remanence (Br) similarly to Example 1 according to condition similarly to Example 1.In addition, calcined temperature is set at 1150 ℃, and firing temperature is set at 1200 ℃.It the results are shown among Figure 36～Figure 38.
As Figure 37 and shown in Figure 38,, when m surpasses 0, can confirm that coercive force (HcJ) is improved using under the situation of Nd as the R element.
The assay value (atom %) of the sintered body of embodiment 1,2,4,12 mades is shown in respectively in Figure 39～42.In addition, in each sintered body, contain Mn, but it is to sneak into the form of the raw material impurity of Fe.And, in each sintered body, contain Ba, but it is to sneak into the form of the raw material impurity of Sr.
Can confirm from the result of above embodiment 1～12, when containing La, also contain in the composition of R that when m surpassed 0, coercive force (HcJ) was improved.But, when m increases, fail to find the effect that this coercive force (HcJ) improves.
But also confirm, when containing La, also contain in the composition of R, when x/yz greater than 1.0 the time, coercive force (HcJ) is improved.
Therefore, according to the present invention, can provide ferrite magnetic material with high magnetic characteristic by containing La and R.
Embodiment 13
In embodiment 13 to Si composition (SiO
2) interpolation period and the relation between the magnetic characteristic study.
The weighing initiation material is so that mainly consist of following composition formula after burning till.
Composition formula: A
1-x(La
1-mR
m)
x(Fe
12-yCo
y)
zO
19
A=Sr wherein, R=Pr
x＝0.12，y＝0.08，z＝1.00
m＝0.33
Then with silica (SiO
2) total amount be constant at 0.6wt%, and with SiO
2Interpolation period, calcined temperature and firing temperature be shown among Figure 43, make sintered body in addition similarly to Example 1, carry out evaluation similarly to Example 1.It the results are shown among Figure 43～Figure 45.In addition, SiO
2Back interpolation be after coarse crushing, to carry out.
As shown in figure 44, along with SiO
2The ratio of preceding addition increase, then remanence (Br) improves, and adds SiO before 100%
2Occasion and the 100% back occasion of adding compare, remanence (Br) improves about 80G raising.And, as shown in figure 45, preceding interpolation SiO
2Can not cause bad influence to coercive force (HcJ).In order to enjoy by preceding interpolation SiO
2The effect that the remanence that is caused (Br) improves is with SiO
240% or above, preferably 50% or above, be more preferably 80% or more than to add before carrying out be effective.
Claims (15)
1, a kind of ferrite sintered magnet is characterized in that, with composition formula: A
1-x(La
1- mR
m)
x(Fe
12-yCo
y)
zO
19Represented composition is a main component,
Wherein, A is select among Sr, Ba and Pb at least a,
R is a kind or 2 kinds among Pr and the Nd,
0.04≤x＜0.80，
0.02≤y≤0.20，
0.00＜m＜0.90，
0.90＜z＜1.10，
1.3≤x/yz＜2.5。
2, ferrite sintered magnet according to claim 1 is characterized in that, in described composition formula, and 0.01≤m≤0.70.
3, ferrite sintered magnet according to claim 1 is characterized in that, in described composition formula, and 0.04≤m≤0.60.
4, ferrite sintered magnet according to claim 1 is characterized in that, in described composition formula, and 0.04≤x≤0.45.
5, ferrite sintered magnet according to claim 1 is characterized in that, in described composition formula, and 0.96≤z≤1.05.
6, ferrite sintered magnet according to claim 1 is characterized in that, must contain Sr as described A.
7, ferrite sintered magnet according to claim 1 is characterized in that, described A is Sr and Ba.
8, ferrite sintered magnet according to claim 1 is characterized in that, described R is Pr.
9, ferrite sintered magnet according to claim 1 is characterized in that, described R is Nd.
10, ferrite sintered magnet according to claim 1 is characterized in that, with respect to described main component, to be converted into SiO
2Meter contains the Si composition of 0.15～1.35wt%, and contains the Ca composition, and the ratio Ca/Si of the mole of the mole of Ca composition and Si composition is 0.35～2.10 scope.
11, ferrite sintered magnet according to claim 1 is characterized in that, described ferrite sintered magnet has above coercive force of 4000Oe and the above remanence Br of 4000G simultaneously.
12, ferrite sintered magnet according to claim 1 is characterized in that, described ferrite sintered magnet has above coercive force of 4500Oe and the above remanence Br of 4200G simultaneously.
13, ferrite sintered magnet according to claim 1 is characterized in that,
0.04≤x≤0.45、
0.02≤y≤0.20、
0.01≤m≤0.70、
0.96≤z≤1.05、
1.3≤x/yz＜2.5。
14, according to claim 1 or 13 described ferrite sintered magnets, it is characterized in that 1.3≤x/yz≤2.3.
15, according to claim 1 or 13 described ferrite sintered magnets, it is characterized in that, with respect to described main component, to be converted into SiO
2Meter contains the Si composition of 0.30～0.90wt%, and contains the Ca composition, and the ratio Ca/Si of the mole of the mole of Ca composition and Si composition is 0.70～1.75 scope.
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| US10027035B2 (en) | 2014-09-30 | 2018-07-17 | Skyworks Solutions, Inc. | Modified Z-type hexagonal ferrite materials with enhanced resonant frequency |
| US10049796B2 (en) | 2014-10-24 | 2018-08-14 | Skyworks Solutions, Inc. | Magnetodielectric Y-phase strontium hexagonal ferrite materials formed by sodium substitution |
| CN105236950A (en) * | 2015-10-12 | 2016-01-13 | 安吉县科声磁性器材有限公司 | High-performance strontium permanent magnetic ferrite preparation method |
| JP6589647B2 (en) * | 2016-01-15 | 2019-10-16 | Tdk株式会社 | Ferrite sintered magnet |
| CN106219610B (en) * | 2016-07-02 | 2017-09-01 | 烟台鑫洋电子有限公司 | A kind of preparation method of Conjugate ferrite nano magnetic material |
| CN107564654A (en) * | 2017-09-15 | 2018-01-09 | 安徽信息工程学院 | A kind of inorganic composite materials IV for magnetic composite and preparation method thereof |
| JP6942379B2 (en) * | 2017-09-25 | 2021-09-29 | 国立研究開発法人産業技術総合研究所 | Magnetic materials and their manufacturing methods |
| CN110511013B (en) * | 2019-08-22 | 2022-02-11 | 兰州理工大学 | La-Ce binary doped barium ferrite wave-absorbing material and preparation method thereof |
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