CN1849675A - Ferrite sintered magnet - Google Patents
Ferrite sintered magnet Download PDFInfo
- Publication number
- CN1849675A CN1849675A CN 200480026243 CN200480026243A CN1849675A CN 1849675 A CN1849675 A CN 1849675A CN 200480026243 CN200480026243 CN 200480026243 CN 200480026243 A CN200480026243 A CN 200480026243A CN 1849675 A CN1849675 A CN 1849675A
- Authority
- CN
- China
- Prior art keywords
- sintered magnet
- burning
- ferrite sintered
- sample
- add
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Hard Magnetic Materials (AREA)
- Magnetic Ceramics (AREA)
Abstract
A ferrite sintered magnet, which has a basic composition represented by the general formula: A1-x-y+aCax+bRy+cFe2n-zCoz+dO19 (atomic ratio)[wherein a,b,c and d are the amounts of A element, Ca, R element and Co, respectively, being added in the step of pulverizing an oxide magnetic material, and are figures satisfying the following requirements: 0.03 <= x <= 0.4, 0.1 <= y <= 0.6, 0 <= z <= 0.4, 4 <= n <= 10, x+y < 1, 0.03 <= x+b <= 0.4, 0.1 <= y+c <= 0.6, 0.1 <= z+d <= 0.4, 0.50 <= [(1-x-y+a)/(1-y+a+b)] <= 0.97, 1.1 <= (y+c)/(z+d) <= 1.8, 1.0 <= (y+c)/x <= 20 and 0.1 <= x/(z+d) <= 1.2.
Description
Technical field
The present invention relates to a kind of high performance ferrite sintered magnet, it is at the magnet application product of wide range, for example extremely useful in the rotating machinery used of automobile or electric equipment, magnet cylinder of used in copy machines etc., compare with ferrite sintered magnet in the past, have higher intrinsic coercive force Hcj and remanence Br.
Background technology
The ferrite sintered magnet of magnetoplumbite type (M type) structure for example is used to motor, generator etc. and comprises in the various uses of rotating machinery.Recently, be purpose at automobile in rotating machinery with the miniaturization and, be purpose at electric machine in rotating machinery with the high efficiency, require ferrite sintered magnet with higher magnetic characteristic.For example, automobile is considered from the viewpoint of miniaturization and with employed ferrite sintered magnet in the rotating machinery, need be made slim product.That is, need be when keeping high Br, not because of the ferrite sintered magnet with high Hcj and high squareness ratio (Hk/Hcj) of the demagnetization degaussing that with the ferrite sintered magnet slimming time, produces.
All the time, M type ferrite sintered magnet such as Sr ferrite or Ba ferrite is utilized following manufacturing process's manufacturing.At first, after the carbonate of iron oxide and Sr or Ba etc. is mixed, utilize pre-burning (Provisional baked) to carry out the ferrite reaction, make the pre-burning clinker.Then,, the specified rate of the meal flour of gained is dropped into atomizer, add SiO in order to control sintering behavior the coarse crushing of pre-burning clinker
2, SrCO
3And CaCO
3Deng, in addition, as required, add Al in order to control Hcj
2O
3Or Cr
2O
3, it is broken to carry out the wet type micro mist, and average grain diameter reaches 0.4～1.2 μ m in solvent.Press molding when the slip that contains the ferrite particulate that makes gained is orientated in magnetic field.Sintering after with the formed body drying of gained is processed as required shape at last.
When adding Al
2O
3Or Cr
2O
3The time, Hcj promptly improves, but Br reduces widely.This phenomenon is because of Al
3+Or Cr
3+M mutually in solid solution and the effect of particle growth when having the effect that reduces saturation magnetization σ s and suppressing sintering causes.
In order to address this problem, the ferrite that No. the 3rd, 337,990, Japan's special permission (corresponding to No. 6139766, United States Patent (USP)) has proposed to have the hexagonal crystal structure is a principal phase, has with A
1-xR
x(Fe
12-yM
y)
zO
19(A is at least a element of selecting from Sr, Ba and Pb, must contain Sr, R is at least a element of selecting from rare earth element (comprising Y), must contain La, M is Co or Co and Zn, and x, y and z satisfy the condition of 0.04≤x≤0.6,0.04≤y≤0.5 and 0.7≤z≤1.2 respectively.) ferrite sintered magnet of composition of expression.According to the record of the embodiment 1 of No. the 3rd, 337,990, Japan's patent, this ferrite sintered magnet is with Fe
2O
3Powder, SrCO
3Powder, Co
3O
4The mixture of powder and CoO powder and La
2O
3Powder cooperates, and adds SiO in addition
2Powder 0.2 quality % and CaCO
3Powder 0.15 quality %, by mix, shaping and sintering are made in the pre-burning, pulverizing, magnetic field.Therefore this manufacturing process is known as " preceding addition manner " owing to add La (R element) and Co (M element) before pre-burning.The ferrite sintered magnet of gained has high Hcj and Br (sample No.11～14).But the squareness ratio Hk/Hcj of sample No.11～14 is lower, reaches 77.6～84.1%.So,, need further to improve magnetic characteristic in order to respond the requirement of described slimming.And, in sample No.11～14, the CaCO in the mixed processes before the pre-burning
3Addition considerably less.
Japan's special permission the 3rd, 262, No. 321 (corresponding to No. 6258290, No. 6086781, United States Patent (USP) and United States Patent (USP)) announces the manufacture method that following hexagonal crystal ferrite sintered magnet is arranged, promptly, having the A element that contains 1～13 atom % in manufacturing (is from Sr, at least a element of selecting among Ba or the Ca, must contain Sr or Ba), 0.05 the R element of～10 atom % (at least a element of from the rare earth element that comprises Y, selecting, perhaps contain Bi therein), 0.1 during the sintered magnet of the composition of the Fe of the M element of～5 atom % (Co or Co and Zn) and 80～95 atom %, in the particle that with the hexagonal crystal ferrite that contains the A element at least is principal phase, add the compound that contains Co and/or R element, perhaps also add the compound that contains Fe and/or A element, its postforming in addition, formally burn till.Therefore this method is known as " back addition manner " because the shredding stage after pre-burning adds R element and M element.But, can be clear that from sample No.1 and 2 ferrite sintered magnet that utilizes this method to obtain can't satisfy the requirement of slimming fully, needs further to improve magnetic characteristic in addition.And, in sample No.1 and 2, the CaCO in the mixed processes before the pre-burning
3Addition considerably less.
No. the 3rd, 181,559, Japan special permission (corresponding to No. 6402980, United States Patent (USP)) announces that having with the hexagonal crystal ferrite is principal phase, has with general formula Ca
1-xR
x(Fe
12-yM
y)
zO
19(R is at least a element of selecting from rare earth element (comprising Y) and Bi, must contain La, and M is Co and/or Ni, and x, y and z satisfy the condition of 0.2≤x≤0.8,0.2≤y≤1.0 and 0.5≤z≤1.2 respectively.) ferrite sintered magnet of composition of expression.But the Hk/Hcj of this ferrite sintered magnet is lower, is 75.9～80.6% (sample No.21～23), can't satisfy the requirement of described slimming.In addition, specially permit the 3rd, 181, shown in Figure 15 of No. 559 and 16, at CaxSr as Japan
(0.4-x)La
0.6Co
0.6Fe
11.4O
19In the composition of (x=0,0.2,0.4), when x reaches 0.4 when above, then magnetic characteristic demonstrates the tendency of reduction.This is because Co content is very many, reaches 0.6.
Announce for Te Kaiping 11-224812 number following ferrite sintered magnet is arranged, it is the ferrite sintered magnet that the M type ferrite coexists mutually with ferrospinel mutually, the M type ferrite is made of the A element (be at least a element of selecting from Sr, Ba or Ca and Pb, must contain Sr and/or Ca) of 1～13 atom %, the R element (at least a element of selecting from rare earth element (comprising Y) and Bi) of 0.05～10 atom %, the M element (metallic elements of divalents such as Co, Zn, Mg, Mn, Cu) of 0.1～5 atom % and the Fe of 80～95 atom %.But, this ferrite sintered magnet since have the M type ferrite mutually with ferrospinel mutually, so magnetic characteristic is poor.
Patent documentation 1: specially permit communique No. 3337990
Patent documentation 2: specially permit communique No. 3262321
Patent documentation 3: specially permit communique No. 3181559
Patent documentation 4: the spy opens flat 11-224812 communique
Summary of the invention
So, the objective of the invention is to, following high performance ferrite sintered magnet is provided, it even have the high intrinsic coercivity H j that slimming also can not reduce, in addition, also has high squareness ratio Hk/Hcj as required when keeping high remanence Br.
The feature of ferrite sintered magnet of the present invention is, has M type ferrite structure, with the A element that is made of Sr or Sr and Ba, as at least a of the rare earth element that contains Y and R element, Ca, Fe and the Co that must contain La is indispensable element, utilization is the operation manufacturing of oxidate magnetic material pulverizing, shaping and sintering, and the basic composition of described oxidate magnetic material is by following general formula (1):
A
1-x-yCa
xR
yFe
2n-zCo
zO
19(atom ratio) ... (1)
Expression, the basic composition of described ferrite sintered magnet are by following general formula (2):
A
1-x-y+aCa
X+bR
Y+cFe
2n-zCo
Z+dO
19(atom ratio) ... (2)
Expression, in described general formula (1) and (2), x, y, z and n represent amount and the mol ratio of Ca, R element and Co in the described oxidate magnetic material respectively, a, b, c and d are illustrated respectively in the amount of the A element, Ca, R element and the Co that add in the pulverizing process of described oxidate magnetic material, are to satisfy following condition respectively:
0.03≤x≤0.4
0.1≤y≤0.6
0≤z≤0.4
4≤n≤10
x+y＜1
0.03≤x+b≤0.4
0.1≤y+c≤0.6
0.1≤z+d≤0.4
0.50≤[(1-x-y+a)/(1-y+a+b)]≤0.97
1.1≤(y+c)/(z+d)≤1.8
1.0≤(y+c)/x≤20 reach
0.1 the numeral of≤x/ (z+d)≤1.2.
Described oxidate magnetic material is a principal phase with M mutually preferably, and preferred especially is the pre-burning body of principal phase with M mutually.
In one embodiment of the present of invention, though utilize after the full dose (1-x-y) (a=0 under this situation) of A element is added in the mixed processes of state before pre-burning of compound, carry out pre-burning, pulverize, manufacturing process's (" preceding additive process of A element ") of shaping and sintering makes ferrite sintered magnet of the present invention, yet stably obtain high magnetic characteristic in order to improve agglutinating property, preferably add in the mixed processes of A element before pre-burning of state with compound, in the pulverizing process of pre-burning body, add the A element of a (a＞0) with the state of compound with (1-x-y).This adding method is called " the front/rear additive process of A element ".
In an alternative embodiment of the invention, though utilize after the full dose x (b=0 under this situation) of Ca is added in the mixed processes of state before pre-burning of compound, the manufacturing process's (" preceding additive process of Ca ") that carries out pre-burning, pulverizing, shaping and sintering makes ferrite sintered magnet of the present invention, yet stably obtain high magnetic characteristic in order to improve agglutinating property, preferably add in the mixed processes of Ca before pre-burning of state with compound, in the pulverizing process of pre-burning body, add the Ca of b (b＞0) with the state of compound with x.This adding method is called " the front/rear additive process of Ca ".
In an alternative embodiment of the invention, in order to obtain the ferrite sintered magnet of high magnetic characteristic, preferably (d=0) add in the mixed processes of state before pre-burning with compound 0.1≤z under this situation≤0.4 with the full dose y (c=0 under this situation) of R element and the full dose z of Co.This adding method is called " the preceding additive process of R element and Co ".
In an alternative embodiment of the invention, in order to obtain the ferrite sintered magnet of high magnetic characteristic, preferably add in the mixed processes of state before pre-burning of a part of z (z under this situation＞0) with the full dose y (c=0 under this situation) of R element and Co with compound, and add in the pulverizing process of state after pre-burning of surplus d (0.1≤z+d under this situation≤0.4, d＞0) with Co with compound.This adding method is called " the preceding interpolation of R element and the front/rear additive process of Co ".
In an alternative embodiment of the invention, in order to obtain the ferrite sintered magnet of high magnetic characteristic, preferably add in the mixed processes of state before pre-burning of full dose y (c=0 under this situation) with the R element with compound, and (z=0) add in the pulverizing process of state after pre-burning with compound 0.1≤d under this situation≤0.4 with the full dose d of Co.This adding method is called " the preceding interpolation of R element and the back additive process of Co ".
In an alternative embodiment of the invention, in order to obtain the ferrite sintered magnet of high magnetic characteristic, preferably with full dose z (0.1≤z under this situation≤0.4 of a part of y and the Co of R element, d=0) add in the mixed processes of state before pre-burning with compound, and add in the pulverizing process of state after pre-burning of surplus c with R with compound.This adding method is called " the front/rear interpolation of R element and the preceding additive process of Co ".
In an alternative embodiment of the invention, in order to obtain the ferrite sintered magnet of high magnetic characteristic, preferably a part of y of R element and a part of z of Co (z under this situation＞0) are added in the mixed processes of state before pre-burning with compound, and the surplus c of R element and the surplus d of Co (0.1≤z+d under this situation≤0.4, d＞0) are added in the pulverizing process of state after pre-burning with compound.This adding method is called " the front/rear interpolation of R element and the front/rear additive process of Co ".
In an alternative embodiment of the invention, in order to obtain the ferrite sintered magnet of high magnetic characteristic, preferably add in the mixed processes of state before pre-burning of a part of y with the R element with compound, and (z=0) add in the pulverizing process of state after pre-burning with compound 0.1≤d under this situation≤0.4 with the surplus c of R element and the full dose d of Co.This adding method is called " the R element: front/rear interpolation, Co: add the back ".
Though the z of the front/rear interpolation of Co and the ratio of d are not particularly limited, be more than 0.02 at d/ (z+d), under the preferred situation more than 0.5, can see the tendency that Br and/or Hcj improve.
Utilize the present invention, can obtain following ferrite sintered magnet, it is when keeping high remanence Br, and the demagnetization degaussing that produces in the time of can be because of slimming has high intrinsic coercivity H j, also has high squareness ratio Hk/Hcj in addition as required.
Description of drawings
Fig. 1 is the figure of an example of the magnetic characteristic of expression ferrite sintered magnet of the present invention.
Fig. 2 is the figure of another example of the magnetic characteristic of expression ferrite sintered magnet of the present invention.
Fig. 3 is the figure of an example of the X-ray diffraction spectrogram of expression ferrite prefiring body of the present invention.
Fig. 4 is the figure of another example of the X-ray diffraction spectrogram of expression ferrite prefiring body of the present invention.
Fig. 5 is the figure of an example of the half range value of (110) face, (107) face in the X-ray diffraction spectrogram of expression ferrite prefiring body of the present invention and (114) face.
Fig. 6 is the figure of another example of the half range value of (110) face, (107) face in the X-ray diffraction spectrogram of expression ferrite prefiring body of the present invention and (114) face.
Fig. 7 is other the figure of example of the magnetic characteristic of expression ferrite sintered magnet of the present invention.
Fig. 8 is other the figure of example of the magnetic characteristic of expression ferrite sintered magnet of the present invention.
Fig. 9 is other the figure of example of the magnetic characteristic of expression ferrite sintered magnet of the present invention.
Figure 10 is other the figure of example of the magnetic characteristic of expression ferrite sintered magnet of the present invention.
Figure 11 is other the figure of example of the magnetic characteristic of expression ferrite sintered magnet of the present invention.
Figure 12 is other the figure of example of the magnetic characteristic of expression ferrite sintered magnet of the present invention.
Figure 13 is other the figure of example of the magnetic characteristic of expression ferrite sintered magnet of the present invention.
Figure 14 is other the figure of example of the magnetic characteristic of expression ferrite sintered magnet of the present invention.
Figure 15 is other the figure of example of the magnetic characteristic of expression ferrite sintered magnet of the present invention.
Figure 16 is other the figure of example of the magnetic characteristic of expression ferrite sintered magnet of the present invention.
Figure 17 is other the figure of example of the magnetic characteristic of expression ferrite sintered magnet of the present invention.
Figure 18 is other the figure of example of the magnetic characteristic of expression ferrite sintered magnet of the present invention.
Embodiment
[1] forms
(A) composition of oxidate magnetic material
Oxidate magnetic material of the present invention preferably with the A element that constitutes by Sr or Sr and Ba, be indispensable element as at least a of the rare earth element that comprises Y and R element, Ca and the Fe that must contain La, and have by following general formula:
A
1-x-yCa
xR
yFe
2n-zCo
zO
19(atom ratio)
The basic composition of expression.Wherein, x, y, z and n represent amount and the mol ratio of Ca, R element and Co respectively, are the numerals that satisfies following condition.
0.03≤x≤0.4
0.1≤y≤0.6
0≤z≤0.4
4≤n≤10
x+y＜1
Though be not particularly limited,, preferably satisfy the condition of 0.55≤[(1-x-y)/(1-y)]≤0.97 and 1.0≤y/x≤20 in order to give good magnetic characteristic to ferrite sintered magnet.When oxidate magnetic material contains Co,, preferably satisfy the condition of 0≤z≤0.4,0.1≤x/z≤1.2 and 1.01≤y/z≤1.8 in order to give good magnetic characteristic to ferrite sintered magnet.
In order to give good magnetic characteristic to ferrite sintered magnet, the Ca content (x) of oxidate magnetic material is preferred 0.03～0.4, and more preferably 0.05～0.3.When x less than 0.03 the time, then Ca is insufficient to the replacement amount of M in mutually, consequently, R becomes insufficient to the displacement of M in mutually, can't obtain the raising effect of magnetic characteristic.When x surpassed 0.4, unreacted CaO increased, and produced α-Fe
2O
3Unfavorable phases such as (bloodstone).
In order to give good magnetic characteristic to ferrite sintered magnet, the R content (y) of oxidate magnetic material is preferred 0.1～0.6, and more preferably 0.15～0.5, preferred especially 0.2～0.4.When y less than 0.1 the time, then insufficient to the replacement amount of M in mutually to R, produce α-Fe
2O
3Etc. unfavorable phase.When y surpassed 0.6, unreacted R oxide increased, and produced α-Fe
2O
3Etc. unfavorable phase.R is at least a of the rare earth elements such as La, Nd, Pr and Ce that comprise Y, must contain La.In order to give good magnetic characteristic to ferrite sintered magnet, more than the preferred 40 atom % of the ratio of the La among the R, more preferably more than the 50 atom %, most preferably more than the 70 atom %, especially preferably use La separately.This be because, the easiest solid solution of La in the middle of the R element in M mutually in.
The Co content (z) of oxidate magnetic material is preferred 0～0.4, and more preferably 0.1～0.3.When z surpassed 0.4, Hcj reduced widely.Though be not particularly limited, when oxidate magnetic material must contain Co, then in order to give good magnetic characteristic to ferrite sintered magnet, the Ca/Co of oxidate magnetic material was than (x/z) preferred 0.1～1.2.When breaking away from this scope, then be difficult to obtain the basic composition of ferrite sintered magnet of the present invention.The R/Co of oxidate magnetic material is than (y/z) preferred 1.01～1.8.When breaking away from this scope, then be difficult to obtain the basic composition of ferrite sintered magnet of the present invention.
The mol ratio n of oxidate magnetic material is preferred 4～10, and more preferably 4.6～7, most preferably 5～6.When n breaks away from 4～10 scope, then be difficult to give good magnetic characteristic to ferrite sintered magnet of the present invention.
When oxidate magnetic material contained the A element, Ca of aequum and R element, ferrite sintered magnet had good magnetic characteristic.So, need satisfy 1-x-y＞0, i.e. the condition of x+y＜1.
The A element is Sr or Sr and Ba.In order to give good magnetic characteristic to ferrite sintered magnet, more than the preferred 51 atom % of the ratio of the Sr among the A, more preferably more than the 70 atom %, most preferably use Sr separately.Though be not particularly limited, the Sr/ of oxidate magnetic material (Sr+Ca) is more preferred 0.55～0.97 than [(1-x-y)/(1-y)], more preferably 0.60～0.95.When (1-x-y)/(1-y) breaks away from 0.55～0.97 scope, then be difficult to obtain the basic composition of ferrite sintered magnet of the present invention.
Though be not particularly limited, the R/Ca of oxidate magnetic material is more preferred 1.0～20 than (y/x), more preferably 1.1～10.When y/x breaks away from 1.0～20 scope, then be difficult to obtain the basic composition of ferrite sintered magnet of the present invention.
(B) composition of ferrite sintered magnet
Ferrite sintered magnet of the present invention, and has with general formula as indispensable element with A element, R element, Ca, Fe and Co: A
1-x-y+aCa
X+bR
Y+cFe
2n-zCo
Z+dO
19The basic composition of (atom ratio) expression.Wherein, a, b, c and d are illustrated respectively in the amount of the A element, Ca, R element and the Co that add in the pulverizing process, are the numerals that satisfies following condition.And x, y, z and n are respectively the content and the mol ratios of the indispensable element of oxidate magnetic material.
0.03≤x≤0.4
0.1≤y≤0.6
0≤z≤0.4
4≤n≤10
x+y＜1
0.03≤x+b≤0.4
0.1≤y+c≤0.6
0.1≤z+d≤0.4
0.50≤[(1-x-y+a)/(1-y+a+b)]≤0.97
1.1≤(y+c)/(z+d)≤1.8
1.0≤(y+c)/x≤20 reach
0.1≤x/(z+d)≤1.2
Though be not particularly limited,, preferably also satisfy the condition of 0≤a≤0.2,0≤b≤0.2,0≤c≤0.5 and 0≤d≤0.4 in order to give good magnetic characteristic to ferrite sintered magnet.That is, in the pulverizing process of ferrite sintered magnet of the present invention, preferably the addition a of A element is 0～0.2, and the addition b of Ca is 0～0.2, and the addition c of R element is 0～0.5, and the addition d of Co is 0～0.4.Here said pulverizing process is meant coarse crushing or the broken operation of micro mist.Though also can surpass the excessive interpolation of described scope, under this situation, opposite magnetic characteristic Br can be reduced to less than 330kA/m less than 410mT or Hcj.So, as long as will produce before this phenomenon soon addition as the higher limit of a, b, c and d.
The mol ratio n ' of ferrite sintered magnet of the present invention can represent according to the basic composition of described ferrite sintered magnet of the present invention, utilizes the relation of n '=(2n+d)/[2 (1+a+b+c)] to try to achieve.Preferred n '=4～6, more preferably 4.5～5.8.If n ' is less than 4, then non magnetic composition increases, and Br reduces widely.When n ' surpasses 6, then produce M phase unfavorable phase (α-Fe in addition
2O
3) etc., magnetic characteristic reduces widely.
The Ca content (x+b) of ferrite sintered magnet of the present invention preferably is made as 0.03～0.4, more preferably is made as 0.05～0.3.If (x+b) less than 0.03, then because Ca is insufficient to the replacement amount of M in mutually, so R just becomes insufficient to the displacement of M phase as a result, can't obtain the raising effect of magnetic characteristic.When (x+b) surpassed 0.4, then unreacted CaO increased, and produced α-Fe
2O
3Etc. unfavorable phase.
The R content (y+c) of ferrite sintered magnet of the present invention is preferred 0.1～0.6, and more preferably 0.15～0.5, preferred especially 0.2～0.4.If (y+c) less than 0.1, then, therefore can't obtain the raising effect of magnetic characteristic because R is insufficient to the replacement amount of M in mutually.If (y+c) surpass 0.6, then unreacted R oxide increases, and produces α-Fe
2O
3Deng.
The Co content (z+d) of ferrite sintered magnet of the present invention preferably is made as 0.1～0.4, more preferably is made as 0.2～0.3.If (z+d) less than 0.1, then can't obtain the raising effect of magnetic characteristic, if surpass at 0.4 o'clock, then Hcj reduces widely.
Represent that [(1-x-y+a)/(1-y+a+b)] of [Sr (Sr+Ca)] ratio of ferrite sintered magnet of the present invention is preferred 0.50～0.97, more preferably 0.60～0.95.When breaking away from described scope, then be difficult to obtain good magnetic characteristic.
Represent that [(y+c)/(z+d)] of (R/Co) ratio of ferrite sintered magnet of the present invention is preferred 1.1～1.8, more preferably 1.2～1.6.When breaking away from described scope, then be difficult to obtain good magnetic characteristic.
Among the present invention, [(y+c)/x] of the ratio of the Ca content of expression R content of ferrite sintered magnet and oxidate magnetic material is preferred 1.0～20, and more preferably 1.1～10.When breaking away from described scope, then be difficult to obtain good magnetic characteristic.
Among the present invention, [x/ (z+d)] of the ratio of the Co content of expression Ca content of oxidate magnetic material and ferrite sintered magnet is preferred 0.1～1.2, and more preferably 0.2～1.1.When breaking away from described scope, then be difficult to obtain good magnetic characteristic.
Among the present invention, though in the basic composition of described oxidate magnetic material and ferrite sintered magnet, the molal quantity of oxygen is made as 19, the value of the chemical theory ratio of components when this is y=z and n=6.Yet, according to kind, pre-burning atmosphere or the firing atmosphere of the valence mumber of Fe and Co, n value, R element, the molal quantity difference of oxygen.Thus, in this specification,, in fact also can how much depart from 19 though the molal quantity of oxygen is expressed as 19.
Among the present invention, when the high Hcj of needs, then effectively way is in the basic composition thing of described ferrite sintered magnet, to represent to add 0.1～3.0% Cr with quality percentage in pulverizing process
2O
3Or Al
2O
3, form thereafter, sintering.If Cr
2O
3Or Al
2O
3Addition less than 0.1%, then can't obtain Hcj and improve effect, when surpassing 3.0%, then Br reduces widely.
[2] manufacture method
(A) manufacturing of oxidate magnetic material
Manufacture method as the oxidate magnetic material with described basic composition (pre-burning body), liquid phase method, separating out of glass method, spray heating decomposition and vapor phase methods such as solid reaction process, coprecipitation, hydrothermal synthesis method can be used alone or in combination, but in the middle of them, solid reaction process more is imbued with practicality.Though also can utilize single corase meal to form oxidate magnetic material, even but for example pre-burning condition and/or pre-burning body are formed the different coarse crushings respectively of the pre-burning body more than 2 kinds, with the corase meal of ratio mixing arbitrarily, as long as have described basic composition.In addition, for example the salvage material (waste material) of formed body or pre-burning body can be used as oxidate magnetic material.Below, be example with solid shaped reaction, the manufacture method of ferrite prefiring body is elaborated.
Gu in the shaped reaction method, as raw material, use croci, comprise the A element powder, comprise the powder of Ca and comprise the powder of R element, use the powder that comprises Co in addition as required, carry out pre-burning (ferriteization) by mixture and make pre-burning body (being generally graininess or clinker) these powder.Pre-burning gets final product in atmosphere, preferably surpasses 0.05atm in partial pressure of oxygen, and special preferred oxygen dividing potential drop is in the atmosphere of 0.1～1.0atm, for example carries out under 1373～1623K 1 second～10 hours, especially preferably carries out about 0.1～3 hour.The pre-burning body that so obtains preferably is made of M in fact mutually.
As the compound of R element, for example use oxide, hydroxide, carbonate or the acylate of R element.On industrial production, use La
2O
3Deng oxide, La (OH)
3Deng hydroxide, La
2(CO
3)
38H
2Carbonate hydrate and La (CH such as O
3CO
2)
31.5H
2O, La
2(C
2O
4)
310H
2Getting final product more than a kind or 2 kinds of acylates such as O, when the oxide, hydroxide, carbonate and the acylate that use cheap mishmetal class (La, Nd, Pr, Ce etc.) more than a kind or 2 kinds the time, then can reduce cost.
As the compound of Co, for example use oxide, hydroxide or the carbonate of Co.On the industrial production, preferably use CoO, Co
3O
4Deng oxide, CoOOH, Co (OH)
2, Co
3O
4M
1H
2O (m
1Be positive number.) wait hydroxide, CoCO
3Deng carbonate and m
2CoCO
3M
3Co (OH)
2M
4H
2Basic carbonate (m such as O
2, m
3, m
4Be positive number.) more than a kind or 2 kinds.
As the compound of Ca, for example use carbonate, the oxide and muriatic more than a kind or 2 kinds of Ca.
As the compound of Sr, for example use carbonate, the oxide and muriatic more than a kind or 2 kinds of Sr.
(B) pulverizing of pre-burning body
To carry out the dry type coarse crushing in the pre-burning body input Roughpulverizer (vibrating roller powder machine or cylinder grind powder machine etc.).Consider the fine load of wet type of back segment etc., preferred 2～5 μ m of the average grain diameter of meal flour.Average grain diameter is to utilize the air penetrant method (determinator: Fischer Sub-Sieve Sizer abbreviates F.S.S.S later on as.) measure with bulk density 65% benchmark.
After the dry type coarse crushing, the meal flour of specified rate and water dropped in the wet type atomizer (grinding mill attritor, ball mill etc.) carry out case of wet attrition.Consider that from the viewpoint that obtains industrial production and high magnetic characteristic the average grain diameter of micro mist flour preferably is made as 0.4～1.2 μ m and (utilizes F.S.S.S to measure with bulk density 65% benchmark.)。When carrying out case of wet attrition to the average grain diameter of ferrite particulate during less than 0.4 μ m, the unusual grain growth during because of sintering, Hcj reduces, and the dehydration characteristic during wet forming worsens in addition.When the average grain diameter of ferrite particulate surpassed 1.2 μ m, then the ratio of the coarse grain in the ferrite cemented body increased, and Hcj reduces.The average grain diameter of micro mist flour more preferably is made as 0.7～1.0 μ m.
When the wet type micro mist is broken, preferably in the basic composition of described ferrite sintered magnet, adds and represent 0.05～1.0% SiO with quality percentage
2By adding SiO
2, can stably obtain high Hcj.This is because utilize SiO
2Interpolation, the particle growth of the M type ferrite particle during sintering is moderately suppressed and can be obtained fine and close tissue of sintered body.If SiO
2Addition less than 0.05%, then can't obtain additive effect, when surpassing 1.0%, then the inhibition effect of particle growth becomes excessive, agglutinating property reduces, the density of sintered body reduces widely.SiO
2Addition more preferably be made as 0.1～0.5%.
After the case of wet attrition, the slip of gained is concentrated and be used for being shaped.Utilize centrifugation or press filtration etc. as long as concentrate.
(C) be shaped
Be shaped and both can have utilized dry type to carry out, also can utilize wet type to carry out.If do not apply ground, magnetic field press molding, then can obtain isotropic ferrite sintered magnet formed body.In order to obtain high magnetic characteristic, preferably apply magnetic field and carry out press molding, can obtain anisotropic ferrite sintered magnet formed body.In order to improve the degree of orientation of formed body, preferably not in dry type magnetic field, to form, but in wet type magnetic field, form.In the wet forming operation, will be shaped in magnetic field is shaped with slip.Forming pressure is made as 0.1～0.5ton/cm
2About get final product, apply magnetic field intensity and be made as about 398～1194kA/m and get final product.
Under the situation of dry pressing, for example described slip is carried out drying or heating (about 323～373K) and, utilize fragmentation such as atomizer then and be used for being shaped water evaporates.Perhaps to described slip is shaped in magnetic field formed body utilize crushing machine etc. to pulverize after, utilize screen cloth to be sized to average grain diameter and reach about 100～700 μ m, form the magnetic field orientating particle, it is shaped in dry type magnetic field.The pressure that is shaped in the dry type magnetic field is made as 0.1～0.5ton/cm
2About get final product, apply magnetic field intensity and be made as about 398～1194kA/m and get final product.
(D) sintering
With formed body air dry in atmosphere, or heating in atmosphere or in the nitrogen atmosphere (373～773K) and remove moisture and the dispersant that added etc.Then, for example in atmosphere, the preferred oxygen dividing potential drop surpasses 0.2atm with formed body, and special preferred oxygen dividing potential drop is in the atmosphere of 0.4～1.0atm, and preferably at 1423～1573K, more preferably the sintering temperature of 1433～1543K is about 0.5～3 hour.The density of ferrite sintered magnet of the present invention is 4.95～5.08g/cm
3About.
[3] characteristic of ferrite sintered magnet
In the section tissue parallel with the c axle of the anisotropic ferrite sintered body of gained, the axial average crystalline particle diameter of c that utilizes scanning electron microscope to measure (is measured 50 M type crystal grain.) below 3 μ m, below the preferred 2 μ m, more preferably 0.5～1.0 μ m.Among the present invention,, also can obtain high Hcj even the average crystalline particle diameter surpasses 1.0 μ m.Among the present invention, give direction as anisotropy with the c direction of principal axis.
Ferrite sintered magnet of the present invention at room temperature for example has the intrinsic coercive force Hcj of remanence Br, 330～478kA/m of 410～460mT and 85～95% the high like this magnetic characteristic of squareness ratio Hk/Hcj.Here, the Parameter H k that is measured when trying to achieve Hk/Hcj is the reading value of H axle of the position of the value that 4 π I reach 0.95Br in the 2nd quadrant of 4 π I (magnetized intensity)-H (intensity in magnetic field) curve.Value (Hk/Hcj) after Hk removed with the Hcj of described demagnetization curve is so-called squareness ratio.
Ferrite sintered magnet of the present invention with aforesaid good magnetic characteristic is very useful in the various motors such as stator, power steering gear or automatically controlled choke valve that automobile is used.In addition, use the magnet cylinder also of great use for the developing roller of used in copy machines.
Below will utilize embodiment to the detailed description of the invention, but the present invention is not limited to these embodiment.
Embodiment 1
The discussion 1 of addition (x) before＜Ca, La and Co are preceding interpolation, Sr is front/rear interpolation 〉
With SrCO
3Powder (containing Ba and Ca), CaCO as impurity
3Powder, La (OH)
3Powder (purity 99.9%), α-Fe
2O
3Powder and Co
3O
4Powder cooperates, and makes it to reach Sr
1-x-yCa
xLa
yFe
2n-zCo
zO
19The basic composition of (n=5.7, y=0.3, z=0.26, x=0.1,0.2 and 0.3).In addition, in complex 100 mass parts, added the SiO of 0.2 mass parts
2Powder.After wet mixed, in atmosphere, 423K dry 24 hours down, pre-burning 1 hour in atmosphere under 1523K then.
The pre-burning body and function roller mill of gained is carried out the dry type coarse crushing, obtained average grain diameter 5 μ m and (utilized F.S.S.S to obtain.) corase meal.The water of the corase meal of 45 quality % and 55 quality % dropped into grinding mill and to carry out the wet type micro mist broken, having obtained containing average grain diameter is that 0.8 μ m (utilizes F.S.S.S to obtain.) the slip of ferrite particulate.At the fine initial stage of wet type,, added the SiO of 0.30 mass parts as sintering aid with respect to corase meal 100 mass parts
2The SrCO of powder, 0.50 mass parts
3The CaCO of powder and 0.80 mass parts (being scaled 0.45 mass parts) with CaO
3Powder.Slip compression molding in the parallel magnetic field of 796kA/m with gained.With the formed body of gained in atmosphere, 1458～1513K at each temperature respectively sintering 2 hours.
The sintered body of gained is processed as the shape of indulging 10mm * horizontal 10mm * thick 20mm, utilizes the BH plotter to measure the magnetic characteristic of room temperature (20 ℃).Measurement result is shown in (△: x=0.1,: x=0.2, : x=0.3) among Fig. 1.In addition, the basic composition of the pre-burning body of gained and sintered body is shown in the hurdle of sample No.2～4 of table 1 and 2.
Example 1 in the past
Identical with embodiment 1, with SrCO
3Powder, CaCO
3Powder, La (OH)
3Powder, α-Fe
2O
3Powder and Co
3O
4Powder cooperates, and makes it to reach Sr
1-x-yCa
xLa
yFe
2n-zCo
zO
19(n=5.7, y=0.3, z=0.26, basic composition x=0).Later on identical with embodiment 1, carry out shaping and sintering in pre-burning, pulverizing, the magnetic field, measured the magnetic characteristic of room temperature of the sintered body of gained.The results are shown among Fig. 1 (zero: x=0).In addition, the basic composition of the pre-burning body of gained and sintered body is shown in the hurdle of sample No.1 of table 1 and 2.
Comparative example 1
Identical with embodiment 1, with SrCO
3Powder, CaCO
3Powder, La (OH)
3Powder, α-Fe
2O
3Powder and Co
3O
4Powder cooperates, and makes it to reach Sr
1-x-yCa
xLa
yFe
2n-zCo
zO
19The basic composition of (n=5.7, y=0.3, z=0.26, x=0.4 and 0.33).Later on identical with embodiment 1, carry out being shaped and sintering in pre-burning, pulverizing, the magnetic field.
Measured the magnetic characteristic of room temperature of the sintered body of gained.With measurement result with Fig. 1's ●, ▲ expression.In addition, the basic composition of the pre-burning body of gained and sintered body is shown among the sample No.30,31 hurdle of table 1 and 2.
[table 1]
| Example No. | Sample No. | n | x | y | z | (1-x-y)/ (1-y) | y/x | x/z | y/z |
| Example 1 in the past | 1 | 5.7 | 0 | 0.3 | 0.26 | 1.0 | - | 0 | 1.15 |
| Embodiment 1 | 2 | 5.7 | 0.1 | 0.3 | 0.26 | 0.86 | 3.0 | 0.38 | 1.15 |
| 3 | 5.7 | 0.2 | 0.3 | 0.26 | 0.71 | 1.5 | 0.77 | 1.15 | |
| 4 | 5.7 | 0.3 | 0.3 | 0.26 | 0.57 | 1.0 | 1.15 | 1.15 | |
| Comparative example 1 | 30 | 5.7 | 0.4 | 0.3 | 0.26 | 0.43 | 0.75 | 1.54 | 1.15 |
| 31 | 5.7 | 0.33 | 0.3 | 0.26 | 0.53 | 0.91 | 1.27 | 1.15 |
[table 2]
| Example No. | Sample No. | a | b | c | d | n′ | x+b | y+c |
| Example 1 in the past | 1 | 0.035 | 0.082 | 0 | 0 | 5.10 | 0.082 | 0.30 |
| Embodiment 1 | 2 | 0.035 | 0.082 | 0 | 0 | 5.10 | 0.082 | 0.30 |
| 3 | 0.035 | 0.082 | 0 | 0 | 5.11 | 0.282 | 0.30 | |
| 4 | 0.034 | 0.081 | 0 | 0 | 5.11 | 0.381 | 0.30 | |
| Comparative example 1 | 30 | 0.034 | 0.081 | 0 | 0 | 5.11 | 0.481 | 0.30 |
| 31 | 0.034 | 0.081 | 0 | 0 | 5.11 | 0.411 | 0.30 |
Table 2 (continuing)
| Example No. | Sample No. | z+d | (1-x-y+a)/ (1-y+a+b) | (y+c) /(z+d) | (y+c)/x | x/(z+d) |
| Example 1 in the past | 1 | 0.26 | 0.90 | 1.15 | - | 0 |
| Embodiment 1 | 2 | 0.26 | 0.78 | 1.15 | 3.00 | 0.38 |
| 3 | 0.26 | 0.65 | 1.15 | 1.50 | 0.77 | |
| 4 | 0.26 | 0.53 | 1.15 | 1.00 | 1.15 | |
| Comparative example 1 | 30 | 0.26 | 0.41 | 1.15 | 0.75 | 1.54 |
| 31 | 0.26 | 0.49 | 1.15 | 0.91 | 1.27 |
Find that according to Fig. 1 and table 1 and 2 ratio of [Sr/ (Sr+Ca)] surpasses the anisotropic ferrite sintered magnet of 49% embodiment 1 and compares with the magnet of example 1 and comparative example 1 in the past and have higher Br and Hcj.
Embodiment 2
The discussion 2 of addition (x) before＜Ca, La and Co are preceding interpolation, Sr is front/rear interpolation 〉
Except the basic composition (addition (x)=0.13,0.25 before the Ca) of the pre-burning body that is made as the sample No.6 shown in the table 3 and 7, made the pre-burning body in the same manner with embodiment 1.Later on carried out in the same manner with embodiment 1 that dry type coarse crushing, wet type micro mist are broken, shaping and sintering in the magnetic field.Measured the magnetic characteristic of room temperature of the anisotropic ferrite sintered magnet of gained.The results are shown among Fig. 2.In addition, the pre-burning body of gained and the basic composition of sintered body are shown in table 3 and 4.
Example 2 in the past
Except the basic composition (addition (x)=0 before the Ca) of the pre-burning body that is made as the sample No.5 shown in the table 3, identical with embodiment 2, carried out that pre-burning, dry type coarse crushing, wet type micro mist are broken, be shaped and sintering in the magnetic field.Measured the magnetic characteristic of room temperature of the anisotropic ferrite sintered magnet of gained.The results are shown among Fig. 2.In addition, the pre-burning body of gained and the basic composition of sintered body are shown in table 3 and 4.
Comparative example 2
Except the basic composition (addition (x)=0.38,0.50 before the Ca) of the pre-burning body that is made as the sample No.8 shown in the table 3 and 9, identical with embodiment 2, carried out that pre-burning, dry type coarse crushing, wet type micro mist are broken, be shaped and sintering in the magnetic field.Measured the magnetic characteristic of room temperature of the anisotropic ferrite sintered magnet of gained.The results are shown among Fig. 2.In addition, the pre-burning body of gained and the basic composition of sintered body are shown in table 3 and 4.
[table 3]
| Example No. | Sample No. | n | x | y | z |
| Example 2 in the past | 5 | 5.42 | 0 | 0.37 | 0.32 |
| Embodiment 2 | 6 | 5.42 | 0.13 | 0.37 | 0.32 |
| 7 | 5.42 | 0.25 | 0.37 | 0.32 | |
| Comparative example 2 | 8 | 5.42 | 0.38 | 0.37 | 0.32 |
| 9 | 5.42 | 0.50 | 0.37 | 0.32 |
Table 3 (continuing)
| Example No. | Sample No. | (1-x-y)/ (1-y) | y/x | x/z | y/z |
| Example 2 in the past | 5 | 1.0 | - | 0 | 1.14 |
| Embodiment 2 | 6 | 0.79 | 2.85 | 0.39 | 1.14 |
| 7 | 0.60 | 1.48 | 0.78 | 1.14 | |
| Comparative example 2 | 8 | 0.40 | 0.97 | 1.17 | 1.14 |
| 9 | 0.21 | 0.74 | 1.56 | 1.14 |
[table 4]
| Example No. | Sample No. | a | b | c | d | n′ | x+b | y+c | z+d |
| Example 2 in the past | 5 | 0.034 | 0.079 | 0 | 0 | 4.87 | 0.079 | 0.37 | 0.32 |
| Embodiment 2 | 6 | 0.033 | 0.079 | 0 | 0 | 4.88 | 0.209 | 0.37 | 0.32 |
| 7 | 0.033 | 0.078 | 0 | 0 | 4.88 | 0.328 | 0.37 | 0.32 | |
| Comparative example 2 | 8 | 0.033 | 0.078 | 0 | 0 | 4.88 | 0.458 | 0.37 | 0.32 |
| 9 | 0.033 | 0.077 | 0 | 0 | 4.88 | 0.577 | 0.37 | 0.32 |
Table 4 (continuing)
| Example No. | Sample No. | (1-x-y+a)/ (1-y+a+b) | (y+c) /(z+d) | (y+c)/x | x/(z+d) |
| Example 2 in the past | 5 | 0.89 | 1.16 | - | 0 |
| Embodiment 2 | 6 | 0.72 | 1.16 | 2.85 | 0.41 |
| 7 | 0.56 | 1.16 | 1.48 | 0.78 | |
| Comparative example 2 | 8 | 0.38 | 1.16 | 0.97 | 1.19 |
| 9 | 0.22 | 1.16 | 0.74 | 1.56 |
Find that according to Fig. 2 the anisotropic ferrite sintered magnet of embodiment 2 (addition (x)=0.13,0.25 before the Ca) is compared with the anisotropic ferrite sintered magnet of example 2 and comparative example 2 in the past, has higher magnetic characteristic.
The X-ray diffraction spectrogram of the pre-burning body of the situation that addition (x) changes before＜the Ca and the magnetic characteristic of anisotropic ferrite sintered magnet, La and Co are preceding interpolation, Sr is front/rear interpolation 〉
Except the basic composition (addition (x)=0.13,0.25 before the Ca) of the pre-burning body that is made as the sample No.66 shown in the table 5 and 67, calcined temperature is made as respectively beyond 1518K and the 1533K, made the pre-burning body in the same manner with embodiment 1.The X-ray diffraction spectrum figure line of the pre-burning body of calcined temperature 1518K is shown among Fig. 3, the X-ray diffraction spectrum figure line of the pre-burning body of calcined temperature 1533K is shown among Fig. 4.X-ray diffraction is that the corase meal with each pre-burning body is fixed in X-ray diffraction device (trade name: RINT-2500, Rigaku Denki Co., Ltd's system), utilizes 2 θ-θ scanning method to measure.In x-ray source, used the CuK alpha ray.The longitudinal axis of Fig. 3 and Fig. 4 is the X-axis diffracted intensity, transverse axis be 2 θ (°).Fig. 5 and Fig. 6 represent (110) face of the pre-burning body of calcined temperature 1518K and 1533K, the half range value that (107) face reaches the diffraction maximum of (114) face respectively.The half range value is the width at peak at 1/2 place of the peak intensity of each diffraction maximum.
Each pre-burning body and embodiment 2 have been carried out in the same manner that dry type coarse crushing, wet type micro mist are broken, have been shaped and sintering in the magnetic field.At room temperature measured the magnetic characteristic of the anisotropic ferrite sintered magnet of gained, consequently, sample No.66 and 67 anisotropic ferrite sintered magnet have roughly equal high Br and the Hcj of anisotropic ferrite sintered magnet (sample No.6 and 7) with embodiment 2.In addition, the basic composition of the pre-burning body of gained and sintered body is shown in the hurdle of sample No.66 in table 5 and 6 and 67.
Example 3 in the past
Except the basic composition (addition (x)=0 before the Ca) of the pre-burning body shown in the hurdle that is made as the sample No.65 shown in the table 5, made the pre-burning body in the same manner with embodiment 3, carried out X-ray diffraction.The X-ray diffraction result is shown in Fig. 3～6.
To the pre-burning body of gained, later operation is identical with embodiment 3, has carried out that dry type coarse crushing, wet type micro mist are broken, has been shaped and sintering in the magnetic field.Measured the magnetic characteristic of room temperature of the anisotropic ferrite sintered magnet of gained, found that compare with the result of embodiment 3, Br and Hcj are lower.In addition, the basic composition of the pre-burning body of gained and sintered body is shown in the hurdle of sample No.65 of table 5 and 6.
Comparative example 3
Except the basic composition (addition (x)=0.38,0.50 before the Ca) of the pre-burning body that is made as the sample No.68 shown in the table 5 and 69, made the pre-burning body in the same manner with embodiment 3, carried out X-ray diffraction.The results are shown in Fig. 3～6.
To the pre-burning body of gained, identical with embodiment 3, carried out that dry type coarse crushing, wet type micro mist are broken, be shaped and sintering in the magnetic field.At room temperature measured the magnetic characteristic of the anisotropic ferrite sintered magnet of gained, found that, compared with the result of embodiment 3, Br and Hcj are lower.In addition, the basic composition of the pre-burning body of gained and sintered body is shown among the sample No.68 and 69 hurdle of table 5 and 6.
[table 5]
| Example No. | Sample No. | n | x | y | z | (1-x-y)/ (1-y) | y/x | x/z | y/z |
| Example 3 in the past | 65 | 5.42 | 0 | 0.37 | 0.32 | 1.0 | - | 0 | 1.14 |
| | 66 | 5.42 | 0.13 | 0.37 | 0.32 | 0.79 | 2.85 | 0.39 | 1.14 |
| 67 | 5.42 | 0.25 | 0.37 | 0.32 | 0.60 | 1.48 | 0.78 | 1.14 | |
| Comparative example 3 | 68 | 5.42 | 0.38 | 0.37 | 0.32 | 0.40 | 0.97 | 1.17 | 1.14 |
| 69 | 5.42 | 0.50 | 0.37 | 0.32 | 0.21 | 0.74 | 1.56 | 1.14 |
[table 6]
| Example No. | Sample No. | a | b | c | d | n′ | x+b | y+c | z+d |
| Example 3 in the past | 65 | 0.034 | 0.079 | 0 | 0 | 4.87 | 0.079 | 0.37 | 0.32 |
| | 66 | 0.033 | 0.079 | 0 | 0 | 4.88 | 0.209 | 0.37 | 0.32 |
| 67 | 0.033 | 0.078 | 0 | 0 | 4.88 | 0.328 | 0.37 | 0.32 | |
| Comparative example 3 | 68 | 0.033 | 0.078 | 0 | 0 | 4.88 | 0.458 | 0.37 | 0.32 |
| 69 | 0.033 | 0.077 | 0 | 0 | 4.88 | 0.577 | 0.37 | 0.32 |
Table 6 (continuing)
| Example No. | Sample No. | (1-x-y+a)/ (1-y+a+b) | (y+c) /(z+d) | (y+c)/x | x/(z+d) |
| Example 3 in the past | 65 | 0.89 | 1.16 | - | 0 |
| | 66 | 0.72 | 1.16 | 2.85 | 0.41 |
| 67 | 0.56 | 1.16 | 1.48 | 0.78 | |
| Comparative example 3 | 68 | 0.38 | 1.16 | 0.97 | 1.19 |
| 69 | 0.22 | 1.16 | 0.74 | 1.56 |
Find that according to Fig. 3 and Fig. 4 the pre-burning body all only is made of M mutually arbitrarily.In addition, can judge that according to Fig. 5 and Fig. 6 the half range value diminishes in 0.13≤x≤0.38, the lattice deformability of crystal is little in 0.13≤x≤0.38.Except that this condition, when forming (0.13≤x≤0.25, [Sr/ (Sr+Ca)] are than=0.60～0.79) at the pre-burning body of having selected embodiment 3, the anisotropic ferrite sintered magnet of gained has high Br and Hcj.That is, do not containing under the too much situation of Ca or Ca content, it is big that lattice deformability becomes, and when required [Sr/ (Sr+Ca)] of disengaging than the time, then the magnetic characteristic of the ferrite sintered magnet of gained is low.
Embodiment 4
The discussion 1:Ca and the Co of addition (y) are preceding interpolation before＜the La, and Sr is front/rear interpolation 〉
Except the basic composition (y=0.30～0.46) of the pre-burning body that is made as sample No.11～15 shown in the table 7, made the anisotropic ferrite sintered magnet in the same manner with embodiment 2, measured the magnetic characteristic of room temperature.Measurement result is shown among Fig. 7.In addition, the pre-burning body of gained and the basic composition of sintered body are shown in table 7 and the table 8.
Comparative example 4
Except the basic composition (y=0.26) of the pre-burning body that is made as the sample No.10 shown in the table 7, made the anisotropic ferrite sintered magnet in the same manner with embodiment 4, measured the magnetic characteristic of room temperature.Measurement result is shown among Fig. 7.In addition, the pre-burning body of gained and the basic composition of sintered body are shown in table 7 and the table 8.
[table 7]
| Example No. | Sample No. | n | x | y | z | (1-x-y)/ (1-y) | y/x | x/z | y/z |
| Comparative example 4 | 10 | 5.7 | 0.1 | 0.26 | 0.26 | 0.86 | 2.6 | 0.38 | 1.00 |
| Embodiment 4 | 11 | 5.7 | 0.1 | 0.30 | 0.26 | 0.86 | 3.0 | 0.38 | 1.15 |
| 12 | 5.7 | 0.1 | 0.34 | 0.26 | 0.85 | 3.4 | 0.38 | 1.31 | |
| 13 | 5.7 | 0.1 | 0.38 | 0.26 | 0.84 | 3.8 | 0.38 | 1.46 | |
| 14 | 5.7 | 0.1 | 0.42 | 0.26 | 0.83 | 4.2 | 0.38 | 1.62 | |
| 15 | 5.7 | 0.1 | 0.46 | 0.26 | 0.81 | 4.6 | 0.38 | 1.77 |
[table 8]
| Example No. | Sample No. | n′ | a | b | c | d | x+b | y+c | z+d |
| Comparative example 4 | 10 | 5.11 | 0.035 | 0.082 | 0 | 0 | 0.182 | 0.26 | 0.26 |
| Embodiment 4 | 11 | 5.11 | 0.035 | 0.082 | 0 | 0 | 0.182 | 0.30 | 0.26 |
| 12 | 5.10 | 0.035 | 0.082 | 0 | 0 | 0.182 | 0.34 | 0.26 | |
| 13 | 5.10 | 0.035 | 0.082 | 0 | 0 | 0.182 | 0.38 | 0.26 | |
| 14 | 5.10 | 0.035 | 0.083 | 0 | 0 | 0.183 | 0.42 | 0.26 | |
| 15 | 5.10 | 0.035 | 0.083 | 0 | 0 | 0.183 | 0.46 | 0.26 |
Table 8 (continuing)
| Example No. | Sample No. | (1-x-y+a)/ (1-y+a+b) | (y+c) /(z+d) | (y+c)/x | x/(z+d) |
| Comparative example 4 | 10 | 0.79 | 1.00 | 2.60 | 0.38 |
| Embodiment 4 | 11 | 0.78 | 1.15 | 3.00 | 0.38 |
| 12 | 0.77 | 1.31 | 3.40 | 0.38 | |
| 13 | 0.75 | 1.46 | 3.80 | 0.38 | |
| 14 | 0.74 | 1.62 | 4.20 | 0.38 | |
| 15 | 0.72 | 1.77 | 4.60 | 0.38 |
Can be clear that from Fig. 7 the anisotropic ferrite sintered magnet that (y/z) of pre-burning body and (y+c)/(z+d) of sintered body are in the embodiment 4 (sample No.11～15) in 1.1～1.8 the scope has high magnetic characteristic.In contrast, (y/z) of the pre-burning body of the anisotropic ferrite magnet of the sample No.10 of comparative example 4 and (y+c)/(z+d) of sintered body are 1.00, and magnetic characteristic is low.
Embodiment 5
The discussion 2:Ca and the Co of addition (y) are preceding interpolation before＜the La, and Sr is front/rear interpolation 〉
Except the basic composition (addition (y)=0.37,0.41 before the La) of the pre-burning body that is made as the sample No.17 shown in the table 9 and 18, carry out in the same manner with embodiment 2 that pre-burning, dry type coarse crushing, wet type micro mist are broken, be shaped and sintering in the magnetic field, make the anisotropic ferrite sintered magnet, at room temperature measured magnetic characteristic.The results are shown among Fig. 8.In addition, the pre-burning body of gained and the basic composition of sintered body are shown in table 9 and the table 10.
Comparative example 5
Except the basic composition (addition (y)=0.32 before the La) of the pre-burning body that is made as the sample No.16 shown in the table 9, made the anisotropic ferrite sintered magnet in the same manner with embodiment 5, at room temperature measured magnetic characteristic.The results are shown among Fig. 8.In addition, the pre-burning body of gained and the basic composition of sintered body are shown in table 9 and the table 10.
[table 9]
| Example No. | Sample No. | n | x | y | z | (1-x-y)/ (1-y) | y/x | x/z | y/z |
| Comparative example 5 | 16 | 5.42 | 0.25 | 0.32 | 0.32 | 0.63 | 1.28 | 0.78 | 1.00 |
| Embodiment 5 | 17 | 5.42 | 0.25 | 0.37 | 0.32 | 0.60 | 1.48 | 0.78 | 1.16 |
| 18 | 5.42 | 0.25 | 0.41 | 0.32 | 0.58 | 1.64 | 0.78 | 1.28 |
[table 10]
| Example No. | Sample No. | a | b | c | d | n′ | x+b | y+c | z+d |
| Comparative example 5 | 16 | 0.033 | 0.078 | 0 | 0 | 4.88 | 0.328 | 0.32 | 0.32 |
| Embodiment 5 | 17 | 0.033 | 0.078 | 0 | 0 | 4.88 | 0.328 | 0.37 | 0.32 |
| 18 | 0.033 | 0.078 | 0 | 0 | 4.88 | 0.328 | 0.41 | 0.32 |
Table 10 (continuing)
| Example No. | Sample No. | (1-x-y+a)/ (1-y+a+b) | (y+c) /(z+d) | (y+c)/x | x/(z+d) |
| Comparative example 5 | 16 | 0.59 | 1.00 | 1.28 | 0.78 |
| Embodiment 5 | 17 | 0.56 | 1.16 | 1.48 | 0.78 |
| 18 | 0.53 | 1.28 | 1.64 | 0.78 |
Can be clear that from Fig. 8 and table 9,10 (y/z) of pre-burning body and (y+c)/(z+d) of sintered body are that the sample No.17 of 1.16 and 1.28 embodiment 5 and 18 anisotropic ferrite sintered magnet have high magnetic characteristic.In contrast, (y+c)/(z+d) of (y/z) of pre-burning body and sintered body is that the magnetic characteristic of anisotropic ferrite sintered magnet of 1.00 comparative example 5 is low.
Embodiment 6
The discussion of＜preceding interpolation Ca amount (x), La amount (y) and Co amount (z), Sr is front/rear interpolation 〉
Basic composition (addition (x)=0.10～0.25 before the Ca except the pre-burning body that is made as sample No.19～22 shown in the table 11, addition (y)=0.29～0.41 before the La, addition (z)=0.24～0.32 before the Co) in addition, carry out in the same manner with embodiment 2 that pre-burning, dry type coarse crushing, wet type micro mist are broken, be shaped and sintering in the magnetic field, made the anisotropic ferrite sintered magnet.The measurement result of the magnetic characteristic under the room temperature is shown among Fig. 9.In addition, the pre-burning body of gained and the basic composition of sintered body are shown in table 11 and 12.
Example 4 in the past
Basic composition (addition (x)=0 before the Ca except the pre-burning body that is made as sample No.23～25 shown in the table 11, addition (y)=0.24～0.37 before the La, addition (z)=0.20～0.32 before the Co) in addition, make the anisotropic ferrite sintered magnet in the same manner with embodiment 6, measured the magnetic characteristic under the room temperature.The results are shown among Fig. 9.In addition, the pre-burning body of gained and the basic composition of sintered body are shown in table 11 and 12.
Comparative example 6
Basic composition (addition (x)=0.52 before the Ca except the pre-burning body that is made as the sample No.26 shown in the table 511, addition (y)=0.48 before the La, addition (z)=0.40, Sr=0 before the Co) in addition, made the anisotropic ferrite sintered magnet in the same manner with embodiment 6.Measured the magnetic characteristic under the room temperature.The results are shown among Fig. 9.In addition, the pre-burning body of gained and the basic composition of sintered body are shown in table 11 and 12.
[table 11]
| Example No. | Sample No. | n | x | y | z | (1-x-y)/ (1-y) | y/x | x/z | y/z |
| Embodiment 6 | 19 | 5.71 | 0.10 | 0.29 | 0.24 | 0.86 | 2.90 | 0.43 | 1.20 |
| 20 | 5.70 | 0.10 | 0.34 | 0.26 | 0.85 | 3.40 | 0.38 | 1.31 | |
| 21 | 5.57 | 0.21 | 0.34 | 0.28 | 0.68 | 1.62 | 0.74 | 1.20 | |
| 22 | 5.42 | 0.25 | 0.41 | 0.32 | 0.58 | 1.64 | 0.78 | 1.28 | |
| Example 4 in the past | 23 | 5.85 | 0 | 0.24 | 0.20 | 1.0 | - | 0 | 1.20 |
| 24 | 5.70 | 0 | 0.30 | 0.26 | 1.0 | - | 0 | 1.15 | |
| 25 | 5.42 | 0 | 0.37 | 0.32 | 1.0 | - | 0 | 1.14 | |
| Comparative example 6 | 26 | 5.15 | 0.52 | 0.48 | 0.40 | 0 | 0.92 | 1.08 | 1.20 |
[table 12]
| Example No. | Sample No. | a | b | c | d | n’ | x+b | y+c | z+d |
| Embodiment 6 | 19 | 0.035 | 0.082 | 0 | 0 | 5.11 | 0.182 | 0.29 | 0.24 |
| 20 | 0.035 | 0.082 | 0 | 0 | 5.10 | 0.182 | 0.34 | 0.26 | |
| 21 | 0.034 | 0.080 | 0 | 0 | 5.00 | 0.290 | 0.34 | 0.28 | |
| 22 | 0.033 | 0.078 | 0 | 0 | 4.88 | 0.328 | 0.41 | 0.32 | |
| Example 4 in the past | 23 | 0.036 | 0.084 | 0 | 0 | 5.23 | 0.084 | 0.24 | 0.20 |
| 24 | 0.035 | 0.082 | 0 | 0 | 5.10 | 0.082 | 0.30 | 0.26 | |
| 25 | 0.034 | 0.079 | 0 | 0 | 4.87 | 0.079 | 0.37 | 0.32 | |
| Comparative example 6 | 26 | 0.031 | 0.074 | 0 | 0 | 4.66 | 0.594 | 0.48 | 0.40 |
Table 12 (continuing)
| Example No. | Sample No. | (1-x-y+a)/ (1-y+a+b) | (y+c) /(z+d) | (y+c)/x | x/(z+d) |
| Embodiment 6 | 19 | 0.78 | 1.21 | 2.90 | 0.42 |
| 20 | 0.77 | 1.31 | 3.40 | 0.38 | |
| 21 | 0.63 | 1.21 | 1.62 | 0.75 | |
| 22 | 0.53 | 1.28 | 1.64 | 0.78 | |
| Example 4 in the past | 23 | 0.90 | 1.20 | - | 0 |
| 24 | 0.90 | 1.15 | - | 0 | |
| 25 | 0.89 | 1.16 | - | 0 | |
| Comparative example 6 | 26 | 0.05 | 1.20 | 0.92 | 1.30 |
As seen from Figure 9, the coarse crushing of pre-burning body, micro mist at the Ca that will contain aequum, La, Co and Sr is broken, be shaped in the magnetic field and the situation of sintering under, the anisotropic ferrite sintered magnet (sample No.19～22 of embodiment 6) that can obtain to have high magnetic characteristic.In contrast, will increase that the coarse crushing of pre-burning soma formula, the wet type micro mist of replacement amount of La and Co is broken without Ca displacement, in the magnetic field shaping and sintering and anisotropic ferrite sintered magnet (sample No.23～25 of example 4 in the past) do not have high magnetic characteristic.In addition, the magnetic characteristic of the anisotropic ferrite magnet of the comparative example 6 (sample No.26) of addition before the Sr=0 is also low.
The discussion 3 of addition (x) before＜Ca, La and Co are preceding interpolation, Sr is front/rear interpolation 〉
Identical with embodiment 1, with SrCO
3Powder, CaCO
3Powder, La (OH)
3Powder, α-Fe
2O
3Powder and Co
3O
4Powder cooperates, and makes it to reach Sr
1-x-yCa
xLa
yFe
2n-zCo
zO
19(n=5.8, x=0.05～0.15, y=0.24, basic composition z=0.2).In complex 100 mass parts of gained, added the SiO of 0.2 mass parts
2Powder.After with the complex wet mixed, in atmosphere, 423K dry 24 hours down, pre-burning 1 hour in atmosphere under 1523K then.
The pre-burning body and function oscillating mode disc type mill of gained is carried out the dry type coarse crushing, obtained average grain diameter 5 μ m and (utilized F.S.S.S to obtain.) corase meal.This corase meal and water dropped into grinding mill and to carry out the wet type micro mist broken, having obtained containing average grain diameter is that 0.8 μ m (utilizes F.S.S.S to obtain.) the slip of ferrite particulate.At the fine initial stage of wet type, in coarse crushing powder 100 weight portions, added the SiO of 0.30 weight portion as sintering aid
2The SrCO of powder, 0.50 weight portion
3The CaCO of powder and 0.80 weight portion (being scaled 0.45 weight portion) with CaO
3Powder.Use the slip of gained, in the parallel magnetic field of 796kA/m, carried out compression molding.With the formed body of gained in atmosphere, under 1458～1513K sintering 2 hours.The sintered body of gained is processed as vertical 10mm * horizontal 10mm * thick 20mm, utilizes the BH plotter to measure the magnetic characteristic of room temperature.Measurement result is shown among Figure 10.In addition, the basic composition of the pre-burning body of gained and sintered body is shown in the hurdle of sample No.102～104 of table 13 and 14.
Example 5 in the past
Except the basic composition with the pre-burning body is made as Sr
1-x-yCa
xLa
yFe
2n-zCo
zO
19(y=0.24 z=0.2) in addition, makes the anisotropic ferrite sintered magnet in the same manner with embodiment 7, has measured the magnetic characteristic of room temperature for n=5.8, x=0.The results are shown among Figure 10.In addition, the basic composition of the pre-burning body of gained and sintered body is shown in the hurdle of sample No.101 of table 13 and 14.
[table 13]
| Example No. | Sample No. | n | x | y | z | (1-x-y)/ (1-y) | y/x | x/z | y/z |
| Example 5 in the past | 101 | 5.8 | 0 | 0.24 | 0.2 | 1.0 | - | 0 | 1.2 |
| | 102 | 5.8 | 0.05 | 0.24 | 0.2 | 0.93 | 4.8 | 0.25 | 1.2 |
| 103 | 5.8 | 0.1 | 0.24 | 0.2 | 0.87 | 2.4 | 0.50 | 1.2 | |
| 104 | 5.8 | 0.15 | 0.24 | 0.2 | 0.80 | 1.6 | 0.75 | 1.2 |
[table 14]
| Example No. | Sample No. | a | b | c | d | n′ | x+b | y+c | z+d |
| Example 5 in the past | 101 | 0.035 | 0.083 | 0 | 0 | 5.19 | 0.083 | 0.24 | 0.20 |
| | 102 | 0.035 | 0.083 | 0 | 0 | 5.19 | 0.133 | 0.24 | 0.20 |
| 103 | 0.035 | 0.083 | 0 | 0 | 5.19 | 0.183 | 0.24 | 0.20 | |
| 104 | 0.035 | 0.083 | 0 | 0 | 5.19 | 0.233 | 0.24 | 0.20 |
Table 14 (continuing)
| Example No. | Sample No. | (1-x-y+a)/ (1-y+a+b) | (y+c) /(z+d) | (y+c)/x | x/(z+d) |
| Example 5 in the past | 101 | 0.91 | 1.20 | - | 0 |
| | 102 | 0.85 | 1.20 | 4.80 | 0.25 |
| 103 | 0.79 | 1.20 | 2.40 | 0.50 | |
| 104 | 0.73 | 1.20 | 1.60 | 0.75 |
Find that according to Figure 10 the anisotropic ferrite sintered magnet of embodiment 7 (sample No.102～104) is compared with example 5 (sample No.101) in the past, has higher magnetic characteristic.
Embodiment 8
The discussion 4 of addition (x) before＜Ca, La and Co are preceding interpolation, Sr is front/rear interpolation 〉
Except the basic composition with the pre-burning body is made as Sr
1-x-yCa
xLa
yFe
2n-zCo
zO
19(y=0.28 z=0.2) in addition, has made the anisotropic ferrite sintered magnet in the same manner with embodiment 7, has measured the magnetic characteristic of room temperature for n=5.8, x=0.05～0.15.Measurement result is shown among Figure 11.In addition, the basic composition of the pre-burning body of gained and sintered body is shown in the hurdle of sample No.106～108 of table 15 and 16.
Example 6 in the past
Except the basic composition with the pre-burning body is made as Sr
1-x-yCa
xLa
yFe
2n-zCo
zO
19(y=0.28 z=0.2) in addition, makes the anisotropic ferrite sintered magnet in the same manner with embodiment 8, has measured the magnetic characteristic of room temperature for n=5.8, x=0.Measurement result is shown among Figure 11.In addition, the basic composition of the pre-burning body of gained and sintered body is shown in the hurdle of sample No.105 of table 15 and 16.
[table 15]
| Example No. | Sample No. | n | x | y | z | (1-x-y)/ (1-y) | y/x | x/z | y/z |
| Example 6 in the past | 105 | 5.8 | 0 | 0.28 | 0.2 | 1.0 | - | 0 | 1.4 |
| Embodiment 8 | 106 | 5.8 | 0.05 | 0.28 | 0.2 | 0.93 | 5.6 | 0.25 | 1.4 |
| 107 | 5.8 | 0.1 | 0.28 | 0.2 | 0.86 | 2.8 | 0.50 | 1.4 | |
| 108 | 5.8 | 0.15 | 0.28 | 0.2 | 0.79 | 1.87 | 0.75 | 1.4 |
[table 16]
| Example No. | Sample No. | a | b | c | d | n′ | x+b | y+c | z+d |
| Example 6 in the past | 105 | 0.035 | 0.084 | 0 | 0 | 5.18 | 0.084 | 0.28 | 0.20 |
| Embodiment 8 | 106 | 0.035 | 0.083 | 0 | 0 | 5.19 | 0.133 | 0.28 | 0.20 |
| 107 | 0.035 | 0.083 | 0 | 0 | 5.19 | 0.183 | 0.28 | 0.20 | |
| 108 | 0.035 | 0.083 | 0 | 0 | 5.19 | 0.233 | 0.28 | 0.20 |
Table 16 (continuing)
| Example No. | Sample No. | (1-x-y+a)/ (1-y+a+b) | (y+c) /(z+d) | (y+c)/x | x/(z+d) |
| Example 6 in the past | 105 | 0.90 | 1.40 | - | 0 |
| Embodiment 8 | 106 | 0.84 | 1.40 | 5.60 | 0.25 |
| 107 | 0.78 | 1.40 | 2.80 | 0.50 | |
| 108 | 0.72 | 1.40 | 1.87 | 0.75 |
Find that according to Figure 11 the anisotropic ferrite sintered magnet of embodiment 8 (sample No.106～108) is compared with example 6 (sample No.105) in the past, has higher magnetic characteristic.
Embodiment 9
The discussion 1 of addition (y) before addition (x) and the La before＜the Ca, Co is preceding interpolation, Sr is front/rear interpolation 〉
Except the basic composition of the pre-burning body that is made as sample No.110～112 shown in the table 17 and sample No.114～116, made the anisotropic ferrite sintered magnet in the same manner with embodiment 7, measured the magnetic characteristic of room temperature.Measurement result is shown among Figure 12.In addition, the pre-burning body of gained and the basic composition of sintered body (sample No.110～112 and sample No.114～116) are shown in table 17 and 18.
Example 7 in the past
Except the basic composition of the pre-burning body that is made as the sample No.109 shown in the table 17 and 113, made the anisotropic ferrite sintered magnet in the same manner with embodiment 9, measured the magnetic characteristic of room temperature.Measurement result is shown among Figure 12.In addition, the pre-burning body of gained and the basic composition of sintered body are shown in table 17 and 18.
[table 17]
| Example No. | Sample No. | n | x | y | z | (1-x-y)/ (1-y) | y/x | x/z | y/z |
| Example 7 in the past | 109 | 5.8 | 0 | 0.29 | 0.24 | 1.0 | - | 0 | 1.2 |
| Embodiment 9 | 110 | 5.8 | 0.05 | 0.29 | 0.24 | 0.93 | 5.8 | 0.21 | 1.2 |
| 111 | 5.8 | 0.10 | 0.29 | 0.24 | 0.86 | 2.9 | 0.42 | 1.2 | |
| 112 | 5.8 | 0.15 | 0.29 | 0.24 | 0.79 | 1.93 | 0.63 | 1.2 | |
| Example 7 in the past | 113 | 5.8 | 0 | 0.34 | 0.24 | 1.0 | - | 0 | 1.4 |
| Embodiment 9 | 114 | 5.8 | 0.05 | 0.34 | 0.24 | 0.92 | 6.8 | 0.21 | 1.4 |
| 115 | 5.8 | 0.10 | 0.34 | 0.24 | 0.85 | 3.4 | 0.42 | 1.4 | |
| 116 | 5.8 | 0.15 | 0.34 | 0.24 | 0.77 | 2.27 | 0.63 | 1.4 |
[table 18]
| Example No. | Sample No. | a | b | c | d | n′ | x+b | y+c | z+d |
| Example 7 in the past | 109 | 0.035 | 0.084 | 0 | 0 | 5.18 | 0.084 | 0.29 | 0.24 |
| Embodiment 9 | 110 | 0.035 | 0.083 | 0 | 0 | 5.18 | 0.133 | 0.29 | 0.24 |
| 111 | 0.035 | 0.083 | 0 | 0 | 5.19 | 0.183 | 0.29 | 0.24 | |
| 112 | 0.035 | 0.083 | 0 | 0 | 5.19 | 0.233 | 0.29 | 0.24 | |
| Example 7 in the past | 113 | 0.036 | 0.084 | 0 | 0 | 5.18 | 0.084 | 0.34 | 0.24 |
| Embodiment 9 | 114 | 0.035 | 0.084 | 0 | 0 | 5.18 | 0.134 | 0.34 | 0.24 |
| 115 | 0.035 | 0.084 | 0 | 0 | 5.18 | 0.184 | 0.34 | 0.24 | |
| 116 | 0.035 | 0.083 | 0 | 0 | 5.19 | 0.233 | 0.34 | 0.24 |
Table 18 (continuing)
| Example No. | Sample No. | (1-x-y+a)/ (1-y+a+b) | (y+c) /(z+d) | (y+c)/x | x/(z+d) |
| Example 7 in the past | 109 | 0.90 | 1.21 | - | 0 |
| Embodiment 9 | 110 | 0.84 | 1.21 | 5.80 | 0.21 |
| 111 | 0.78 | 1.21 | 2.90 | 0.42 | |
| 112 | 0.72 | 1.21 | 1.93 | 0.63 | |
| Example 7 in the past | 113 | 0.89 | 1.42 | - | 0 |
| Embodiment 9 | 114 | 0.83 | 1.42 | 6.80 | 0.21 |
| 115 | 0.76 | 1.42 | 3.40 | 0.42 | |
| 116 | 0.70 | 1.42 | 2.27 | 0.63 |
Find that according to Figure 12 the anisotropic ferrite sintered magnet of embodiment 9 (sample No.110～112 and sample No.114～116) is compared with example 7 (sample No.109,113) in the past, has higher magnetic characteristic.
Embodiment 10
The discussion 2 of addition (y) before addition (x) and the La before＜the Ca, Co is preceding interpolation, Sr is front/rear interpolation 〉
Except the basic composition of the pre-burning body that is made as the sample No.40 shown in the table 19, made the anisotropic ferrite sintered magnet in the same manner with embodiment 10, measured the magnetic characteristic of room temperature.Measurement result is shown among Figure 13.In addition, the pre-burning body of gained and the basic composition of sintered body are shown in table 19 and 20.
[table 19]
| Example No. | Sample No. | n | x | y | z | (1-x-y)/ (1-y) | y/x | x/z | y/z |
| Embodiment 10 | 117 | 5.8 | 0.10 | 0.39 | 0.28 | 0.84 | 3.9 | 0.36 | 1.4 |
| 118 | 5.8 | 0.15 | 0.39 | 0.28 | 0.75 | 2.6 | 0.54 | 1.4 | |
| 119 | 5.8 | 0.20 | 0.39 | 0.28 | 0.67 | 1.95 | 0.71 | 1.4 | |
| 120 | 5.8 | 0.10 | 0.45 | 0.28 | 0.82 | 4.5 | 0.36 | 1.6 | |
| 121 | 5.8 | 0.15 | 0.45 | 0.28 | 0.73 | 3.0 | 0.54 | 1.6 | |
| 122 | 5.8 | 0.20 | 0.45 | 0.28 | 0.64 | 2.25 | 0.71 | 1.6 | |
| Comparative example 7 | 40 | 5.8 | 0 | 0.45 | 0.28 | 1.0 | - | - | 1.6 |
[table 20]
| Example No. | Sample No. | a | b | c | d | n′ | x+b | y+c | z+d |
| Embodiment 10 | 117 | 0.036 | 0.084 | 0 | 0 | 5.18 | 0.184 | 0.39 | 0.28 |
| 118 | 0.035 | 0.084 | 0 | 0 | 5.18 | 0.234 | 0.39 | 0.28 | |
| 119 | 0.035 | 0.083 | 0 | 0 | 5.19 | 0.283 | 0.39 | 0.28 | |
| 120 | 0.036 | 0.084 | 0 | 0 | 5.18 | 0.184 | 0.45 | 0.28 | |
| 121 | 0.036 | 0.084 | 0 | 0 | 5.18 | 0.234 | 0.45 | 0.28 | |
| 122 | 0.035 | 0.084 | 0 | 0 | 5.18 | 0.284 | 0.45 | 0.28 | |
| Comparative example 7 | 40 | 0.036 | 0.084 | 0 | 0 | 5.18 | 0.084 | 0.45 | 0.28 |
Table 20 (continuing)
| Example No. | Sample No. | (1-x-y+a)/ (1-y+a+b) | (y+c) /(z+d) | (y+c)/x | x/(z+d) |
| Embodiment 10 | 117 | 0.75 | 1.39 | 3.90 | 0.36 |
| 118 | 0.68 | 1.39 | 2.60 | 0.54 | |
| 119 | 0.61 | 1.39 | 1.95 | 0.71 | |
| 120 | 0.73 | 1.61 | 4.50 | 0.36 | |
| 121 | 0.65 | 1.61 | 3.00 | 0.54 | |
| 122 | 0.58 | 1.61 | 2.25 | 0.71 | |
| Comparative example 7 | 40 | 0.87 | 1.61 | - | 0 |
Find that according to Figure 13 the anisotropic ferrite sintered magnet of embodiment 10 is compared with the magnet of comparative example 7, has higher magnetic characteristic.
Embodiment 11
＜Ca, La and Co are front/rear interpolation, and Sr is preceding interpolation 〉
Except using SrCO in the same manner with embodiment 1
3Powder, CaCO
3Powder, La (OH)
3Powder, α-Fe
2O
3Powder and Co
3O
4Powder is made as beyond the basic composition of pre-burning body of sample No.124～126 shown in the table 21, has made the pre-burning body in the same manner with embodiment 1.And, in the wet mixed operation before pre-burning, in mixture 100 mass parts, added the SiO of 0.2 mass parts
2Powder.With pre-burning soma formula coarse crushing to the average grain diameter of gained is that 5 μ m (utilize F.S.S.S to obtain.)。Then, utilize grinding mill that described corase meal wet type micro mist is broken, having obtained having disperseed average grain diameter is that 0.8 μ m (utilizes F.S.S.S to obtain.) the slip of ferrite particulate.At the described fine initial stage, in described corase meal 100 mass parts that drop into grinding mill, added the La (OH) of 0.933 mass parts
3The Co of powder, 0.4 mass parts
3O
4The CaCO of powder, 0.8 mass parts
3The SiO of powder and 0.3 mass parts
2Powder.Use the slip of gained, carry out in the same manner being shaped and sintering in the magnetic field, at room temperature measured the magnetic characteristic of the anisotropic ferrite sintered magnet of gained with embodiment 1.The results are shown among Figure 14.Will be in atmosphere, under 1473K and the 1483K respectively magnetic characteristic and the axial average crystalline particle diameter of c under the room temperature of the anisotropic ferrite sintered magnet of the sample No.124 of sintering (50 of M type crystal grain are measured.) be shown in the table 23.In addition, the pre-burning body of gained and the basic composition of sintered body are shown in table 21 and 22.
Embodiment 12
＜Ca and Sr are front/rear interpolation, and La and Co are preceding interpolation 〉
Except identical, with SrCO with embodiment 1
3Powder, CaCO
3Powder, La (OH)
3Powder, α-Fe
2O
3Powder and Co
3O
4Powder cooperates, and makes it to reach beyond the basic composition of pre-burning body of the sample No.127 shown in the table 21, has made the pre-burning body in the same manner with embodiment 1.And, in the wet mixed operation before pre-burning, in mixture 100 mass parts, added the SiO of 0.2 mass parts
2Powder.With pre-burning soma formula coarse crushing to the average grain diameter of gained is that 5 μ m (utilize F.S.S.S to obtain.)。
Described corase meal and water are dropped into grinding mill, and it is broken to carry out the wet type micro mist, and having obtained having disperseed average grain diameter is that 0.8 μ m (utilizes F.S.S.S to obtain.) the slip of ferrite particulate.At the described fine initial stage, in described corase meal 100 mass parts that drop into grinding mill, added the SrCO of 0.5 mass parts
3The CaCO of powder, 0.8 mass parts
3The SiO of powder and 0.3 mass parts
2Powder.
Use the slip of gained, carry out in the same manner being shaped and sintering in the magnetic field, measured the magnetic characteristic under the room temperature of anisotropic ferrite sintered magnet of gained with embodiment 1.Measurement result is represented with the figure line of the sample No.127 of Figure 14.To distinguish the magnetic characteristic and the axial average crystalline particle diameter of c of room temperature of anisotropic ferrite sintered magnet of the sample No.127 of sintering under 1473K and 1483K (measures 50 of M type crystal grain.) be shown in the table 23.In addition, the basic composition of the pre-burning body of gained and sintered body is shown in the hurdle of sample No.127 of table 21 and 22.
Example 8 in the past
Except the basic composition with the pre-burning body is made as the composition of the No.123 shown in the table 21, make the anisotropic ferrite sintered magnet in the same manner with embodiment 1, measured the magnetic characteristic of room temperature.Measurement result is shown among Figure 14.In addition, the basic composition of the pre-burning body of gained and sintered body is shown in the hurdle of sample No.123 of table 21 and 22.
[table 21]
| Example No. | Sample No. | n | x | y | z | (1-x-y)/ (1-y) | y/x | x/z | y/z | x+b |
| Example 8 in the past | 123 | 5.8 | 0 | 0.16 | 0.15 | 1.0 | - | 0 | 1.1 | 0.083 |
| Embodiment 11 | 124 | 5.8 | 0.05 | 0.17 | 0.15 | 0.94 | 3.4 | 0.34 | 1.2 | 0.133 |
| 125 | 5.8 | 0.05 | 0.23 | 0.19 | 0.94 | 4.6 | 0.26 | 1.2 | 0.133 | |
| 126 | 5.8 | 0.10 | 0.27 | 0.19 | 0.86 | 2.7 | 0.53 | 1.4 | 0.183 | |
| Embodiment 12 | 127 | 5.8 | 0.05 | 0.21 | 0.19 | 0.94 | 4.2 | 0.26 | 1.1 | 0.133 |
[table 22]
| Example No. | Sample No. | a | b | c | d | n′ | y+c | z+d |
| Example 8 in the past | 123 | 0 | 0.083 | 0.051 | 0.052 | 5.14 | 0.211 | 0.202 |
| Embodiment 11 | 124 | 0 | 0.083 | 0.051 | 0.052 | 5.14 | 0.221 | 0.202 |
| 125 | 0 | 0.083 | 0.051 | 0.052 | 5.14 | 0.281 | 0.242 | |
| 126 | 0 | 0.083 | 0.051 | 0.052 | 5.14 | 0.321 | 0.242 | |
| Embodiment 12 | 127 | 0.035 | 0.083 | 0 | 0 | 5.19 | 0.210 | 0.190 |
Table 22 (continuing)
| Example No. | Sample No. | (1-x-y+a)/ (1-y+a+b) | (y+c) /(z+d) | (y+c)/x | x/(z+d) |
| Example 8 in the past | 123 | 0.91 | 1.04 | - | 0 |
| Embodiment 11 | 124 | 0.85 | 1.09 | 4.42 | 0.25 |
| 125 | 0.84 | 1.16 | 5.62 | 0.21 | |
| 126 | 0.77 | 1.33 | 3.21 | 0.41 | |
| Embodiment 12 | 127 | 0.85 | 1.11 | 4.20 | 0.26 |
[table 23]
| Example No. | Sample No. | Sintering temperature (K) | Br (mT) | Hcj (kA/m) | Hk/Hcj (％) | Average crystalline particle diameter (μ m) |
| Embodiment 11 | 124 | 1473 | 431 | 377.8 | 89.6 | 0.98 |
| 1483 | 434 | 357.5 | 90.6 | 1.02 | ||
| Embodiment 12 | 127 | 1473 | 429 | 358.7 | 87.9 | 0.99 |
| 1483 | 434 | 343.9 | 88.4 | 1.02 |
Find according to Figure 14 and table 21～23, add Ca, La and the Co of specified rate in the mixed processes before pre-burning, and then add Ca, La and the Co of specified rate in the pulverizing process after pre-burning, carry out shaping and sintering in the magnetic field thereafter and anisotropic ferrite sintered magnet (La and the Co: front/rear interpolation) compare, have higher magnetic characteristic of embodiment 11 (sample No.124～126) with the magnet of example 8 (sample No.123) in the past.
Find according to Figure 14 and table 23, embodiment 11 (sample No.124, La and Co: (sample No.127, La and Co: anisotropic ferrite sintered magnet front/rear interpolation) is compared with embodiment 12 by anisotropic ferrite sintered magnet preceding interpolation), Br is more than equal extent, and Hcj reaches (Hk/Hcj) higher.In addition, find that the anisotropic ferrite sintered magnet of embodiment 12 (sample No.127) is compared with the magnet of example 8 (sample No.123) in the past, has higher magnetic characteristic according to Figure 14.
Embodiment 13
The comparison of adding behind front/rear interpolation of＜Ca and the Ca, La and Co are preceding interpolation 〉
Except the basic composition of the pre-burning body that is made as the sample No.128 shown in the table 24, carry out in the same manner with embodiment 1 that pre-burning, coarse crushing, wet type micro mist are broken, be shaped and sintering in the magnetic field, make the anisotropic ferrite sintered magnet, measured the magnetic characteristic of room temperature.Measurement result is shown among Figure 15.In addition, the basic composition of the pre-burning body of gained and sintered body is shown in the hurdle of sample No.128 of table 24 and 25.
Comparative example 8
Except the basic composition of the pre-burning body that is made as the sample No.129 shown in the table 24 and 130, pre-burning and coarse crushing have been carried out in the same manner with embodiment 1.The corase meal and the water of the gained of specified rate are dropped into grinding mill, and it is broken to have carried out the wet type micro mist.At the fine initial stage of wet type, in corase meal 100 mass parts that dropped into grinding mill, added the SrCO that table 26 is put down in writing
3Powder, CaCO
3Powder and SiO
2Powder.And, shown in table 26, according to the roughly the same mode of basic composition that makes sample No.128,129 and 130 sintered body, the CaCO when making the wet type micro mist of sample No.129 and 130 broken
3Addition is the CaCO when broken more than the wet type micro mist of sample No.128
3Addition.Use the slip that contains the ferrite particulate of gained, carry out in the same manner being shaped and sintering in the magnetic field with embodiment 1.Measured the magnetic characteristic of room temperature of the anisotropic ferrite sintered magnet of gained.The results are shown among Figure 15.In addition, the basic composition of the pre-burning body of gained and sintered body is shown among the sample No.129 and 130 hurdle of table 24 and 25.
Example 9 in the past
Except the basic composition of the pre-burning body that is made as the No.131 shown in the table 24, carried out in the same manner with embodiment 1 that pre-burning, coarse crushing, wet type micro mist are broken, be shaped and sintering in the magnetic field.And shown in table 24～26, the pre-burning body of sample No.131 does not contain Ca, and the CaCO of micro mist when broken
3Addition is identical with sample No.128.Therefore, the Ca content of the sintered body of sample No.131 is lower than sample No.128～130.Measured the magnetic characteristic of room temperature of the anisotropic ferrite sintered magnet of gained.The results are shown among Figure 15.In addition, the basic composition of the pre-burning body of gained and sintered body is shown in the hurdle of sample No.131 of table 24 and 25.
[table 24]
| Example No. | Sample No. | n | x | y | z | (1-x-y)/ (1-y) | y/x | x/z | y/z |
| Embodiment 13 | 128 | 5.76 | 0.05 | 0.23 | 0.19 | 0.94 | 4.6 | 0.26 | 1.20 |
| Comparative example 8 | 129 | 5.85 | 0 | 0.23 | 0.20 | 1.0 | - | 0 | 1.20 |
| 130 | 6.06 | 0 | 0.24 | 0.20 | 1.0 | - | 0 | 1.20 | |
| Example 9 in the past | 131 | 5.76 | 0 | 0.21 | 0.19 | 1.0 | - | 0 | 1.20 |
[table 25]
| Example No. | Sample No. | a | b | c | d | n′ | x+b | y+c | z+d |
| Embodiment 13 | 128 | 0.035 | 0.083 | 0 | 0 | 5.15 | 0.133 | 0.23 | 0.19 |
| Comparative example 8 | 129 | 0 | 0.135 | 0 | 0 | 5.15 | 0.135 | 0.23 | 0.20 |
| 130 | 0.037 | 0.139 | 0 | 0 | 5.15 | 0.139 | 0.24 | 0.20 | |
| Example 9 in the past | 131 | 0.035 | 0.083 | 0 | 0 | 5.15 | 0.083 | 0.21 | 0.19 |
Table 25 (continuing)
| Example No. | Sample No. | (1-x-y+a)/ (1-y+a+b) | (y+c) /(z+d) | (y+c)/x | x/(z+d) |
| Embodiment 13 | 128 | 0.85 | 1.21 | 4.60 | 0.26 |
| Comparative example 8 | 129 | 0.85 | 1.15 | - | 0 |
| 130 | 0.85 | 1.20 | - | 0 | |
| Example 9 in the past | 131 | 0.91 | 1.11 | - | 0 |
[table 26]
| Example No. | Sample No. | SrCO 3(quality %) | CaCO 3(quality %) | SiO 2(quality %) |
| Embodiment 13 | 128 | 0.5 | 0.8 | 0.3 |
| Comparative example 8 | 129 | 0 | 1.28 | 0.3 |
| 130 | 0.5 | 1.28 | 0.3 | |
| Example 9 in the past | 131 | 0.5 | 0.8 | 0.3 |
From Figure 15, can find to have the highest magnetic characteristic by the anisotropic ferrite sintered magnet (sample No.128) that adds the embodiment 13 that specified rate Ca makes in the mixed processes before pre-burning.Promptly, added in the pulverizing process after pre-burning in the anisotropic ferrite sintered magnet (sample No.129 and 130) of comparative example 8 of the suitable Ca amount of Ca content with embodiment 13, though can obtain the raising effect of magnetic characteristic to a certain degree, magnetic characteristic is compared low with embodiment 13 (sample No.128).Do not add in the mixed processes before pre-burning in the anisotropic ferrite sintered magnet (sample No.131) of the example in the past 9 of Ca, compare with embodiment 13 (sample No.128) and comparative example 8 (sample No.129 and 130), magnetic characteristic reduces.
In Figure 15, compare embodiment 13 (sample No.128) with comparative example 8 (sample No.129 and 130) though the higher reason of magnetic characteristic uncertain clear and definite, can followingly consider.A side who has added Ca (embodiment 13) in the mixed processes before pre-burning with in pulverizing process, added Ca (comparative example 8) and compared, the ratio that is replaced into the M phase is more, the side of embodiment 13 compares with comparative example 8 thus, be replaced into the La of M phase and the ratio of Co and improve, can realize high magnetic characteristic.
Embodiment 14
＜Ca, La and Co are preceding interpolation, and Sr is that add the back 〉
The Sr that basic composition is with specified rate
1-x-yCa
xLa
yFe
2n-zCo
zO
19(n=5.8, x=0.10, y=0.34, the pre-burning body corase meal of the sample No.115 (with reference to table 17) of embodiment 9 z=0.24) and the input grinding mill of water, it is broken to carry out the wet type micro mist, and having obtained containing average grain diameter is that 0.8 μ m (utilizes F.S.S.S to obtain.) the slip of ferrite particulate.At the fine initial stage of wet type, in corase meal 100 mass parts that drop into grinding mill, added the SrCO of 1.68 mass parts
3The SiO of powder and 0.30 mass parts
2Powder.Later and embodiment 1 has made the anisotropic ferrite sintered magnet in the same manner.Magnetic characteristic under the room temperature of the sintered body of gained is shown in the table 27.In addition, the basic composition of the pre-burning body of gained and sintered body is shown in the hurdle of sample No.141 of table 28 and 29.
[table 27]
| Example No. | Sample No. | Sintering temperature (K) | Br (mT) | Hcj (kA/m) |
| Embodiment 14 | 141 | 1493 | 428 | 378.0 |
| Example 7 in the past | 113 | 1483 | 426 | 371.6 |
| Embodiment 9 | 115 | 1493 | 433 | 389.1 |
[table 28]
| Example No. | Sample No. | n | x | y | z | (1-x-y)/ (1-y) | y/x | x/z | y/z |
| Embodiment 14 | 141 | 5.8 | 0.10 | 0.34 | 0.24 | 0.85 | 3.4 | 0.42 | 1.4 |
| Example 7 in the past | 113 | 5.8 | 0 | 0.34 | 0.24 | 1.0 | - | 0 | 1.4 |
| Embodiment 9 | 115 | 5.8 | 0.10 | 0.34 | 0.24 | 0.85 | 3.4 | 0.42 | 1.4 |
[table 29]
| Example No. | Sample No. | a | b | c | d | n′ | x+b | y+c | z+d |
| Embodiment 14 | 141 | 0.119 | 0 | 0 | 0 | 5.18 | 0.10 | 0.34 | 0.24 |
| Example 7 in the past | 113 | 0.036 | 0.084 | 0 | 0 | 5.18 | 0.084 | 0.34 | 0.24 |
| Embodiment 9 | 115 | 0.035 | 0.084 | 0 | 0 | 5.18 | 0.184 | 0.34 | 0.24 |
Table 29 (continuing)
| Example No. | Sample No. | (1-x-y+a)/ (1-y+a+b) | (y+c) /(z+d) | (y+c)/x | x/(z+d) |
| Embodiment 14 | 141 | 0.87 | 1.42 | 3.4 | 0.42 |
| Example 7 in the past | 113 | 0.89 | 1.42 | - | 0 |
| Embodiment 9 | 115 | 0.76 | 1.42 | 3.4 | 0.42 |
Find that according to table 27～29 the preceding anisotropic ferrite sintered magnet (sample No.141) of the embodiment 14 of Ca that added is compared with routine (sample No.113) in the past, magnetic characteristic is higher.
＜La: preceding interpolation, Co: preceding interpolation 〉
Identical with embodiment 1, utilize SrCO
3Powder, CaCO
3Powder, La (OH)
3Powder, α-Fe
2O
3Powder and CoOOH powder carry out wet mixed and pre-burning (in the atmosphere, 1523K, 1 hour), have made the pre-burning body of the basic composition of the sample No.151 shown in the table 30.And, in described wet type operation, with respect to the SiO that has added 0.2 mass parts in wet mixed thing 100 mass parts
2Powder.With pre-burning soma formula coarse crushing to the average grain diameter of gained is that 5 μ m (utilize F.S.S.S to obtain.), it is broken to carry out the wet type micro mist then, and having obtained having disperseed average grain diameter is that 0.8 μ m (utilizes F.S.S.S to obtain.) the slip of ferrite particulate.At the fine initial stage, added the CaCO of 1.10 mass parts respectively with respect to corase meal 100 mass parts that drop into grinding mill
3The SiO of powder and 0.3 mass parts
2Powder.Utilize the slip of gained, carry out being shaped and sintering (in the atmosphere, 1458～1513K, 2 hours) in the magnetic field.Measured the magnetic characteristic of room temperature of the anisotropic ferrite sintered magnet of gained.The results are shown in the figure line of sample No.151 of Figure 16.In addition, the basic composition of the pre-burning body of gained and sintered body is shown in the hurdle of table 30,31 sample No.151.
Embodiment 16
＜La: preceding interpolation, Co: front/rear interpolation 〉
Identical with embodiment 15, made the pre-burning body of the basic composition of the sample No.152 shown in the table 30, carried out the dry type coarse crushing.Then, drop into the described corase meal and the water of specified rate in grinding mill, it is broken to carry out the wet type micro mist, and having obtained having disperseed average grain diameter is that 0.8 μ m (utilizes F.S.S.S to obtain.) the slip of ferrite particulate.At the fine initial stage, the CoOOH powder of 1.07 mass parts, the CaCO of 1.11 mass parts have been added respectively with respect to corase meal 100 mass parts that drop into grinding mill
3The SiO of powder and 0.3 mass parts
2Powder.Later on identical with embodiment 15, utilize the slip of gained, carry out shaping and sintering in the magnetic field.Measured the magnetic characteristic of room temperature of the anisotropic ferrite sintered magnet of gained.Measurement result is shown in the figure line of sample No.152 of Figure 16.In addition, the basic composition of the pre-burning body of gained and sintered body is shown in the hurdle of table 30,31 sample No.152.
Embodiment 17
＜La: preceding interpolation, Co: add the back 〉
Identical with embodiment 15, made the pre-burning body of the basic composition of the sample No.153 shown in the table 30, carried out the dry type coarse crushing.Then, drop into the described corase meal and the water of specified rate in grinding mill, it is broken to carry out the wet type micro mist, and having obtained having disperseed average grain diameter is that 0.8 μ m (utilizes F.S.S.S to obtain.) the slip of ferrite particulate.At the fine initial stage, the CoOOH powder of 2.15 mass parts, the CaCO of 1.12 mass parts have been added respectively with respect to corase meal 100 mass parts that drop into grinding mill
3The SiO of powder and 0.3 mass parts
2Powder.Later on identical with embodiment 15, utilize the slip of gained, carry out shaping and sintering in the magnetic field.Measured the magnetic characteristic of room temperature of the anisotropic ferrite sintered magnet of gained.Measurement result is shown in the figure line of sample No.153 of Figure 16.In addition, the basic composition of the pre-burning body of gained and sintered body is shown in the hurdle of table 30,31 sample No.153.
Embodiment 18
＜La: front/rear interpolation, Co: preceding interpolation 〉
Identical with embodiment 15, made the pre-burning body of the basic composition of the sample No.154 shown in the table 30, carried out the dry type coarse crushing.Then, drop into the described corase meal and the water of specified rate in grinding mill, it is broken to carry out the wet type micro mist, and having obtained having disperseed average grain diameter is that 0.8 μ m (utilizes F.S.S.S to obtain.) the slip of ferrite particulate.At the fine initial stage, added the La (OH) of 0.47 mass parts respectively with respect to corase meal 100 mass parts that drop into grinding mill
3The CaCO of powder, 1.08 mass parts
3The SiO of powder and 0.3 mass parts
2Powder.Later on identical with embodiment 15, utilize the slip of gained, carry out shaping and sintering in the magnetic field, measured the magnetic characteristic of room temperature of the anisotropic ferrite sintered magnet of gained.Measurement result is shown in the figure line of sample No.154 of Figure 16.In addition, the basic composition of the pre-burning body of gained and sintered body is shown in the hurdle of table 30,31 sample No.154.
Embodiment 19
＜La: front/rear interpolation, Co: add the back 〉
Identical with embodiment 15, made the pre-burning body of the basic composition of the sample No.155 shown in the table 30, carried out the dry type coarse crushing.Then, drop into the described corase meal and the water of specified rate in grinding mill, it is broken to carry out the wet type micro mist, and having obtained having disperseed average grain diameter is that 0.8 μ m (utilizes F.S.S.S to obtain.) the slip of ferrite particulate.At the fine initial stage, added the La (OH) of 0.47 mass parts respectively with respect to corase meal 100 mass parts that drop into grinding mill
3The CoOOH powder of powder, 2.07 mass parts and the SiO of 0.3 mass parts
2Powder.Later on identical with embodiment 15, utilize the slip of gained, carry out shaping and sintering in the magnetic field.Measured the magnetic characteristic of room temperature of the anisotropic ferrite sintered magnet of gained.Measurement result is shown in the figure line of sample No.155 of Figure 16.In addition, the basic composition of the pre-burning body of gained and sintered body is shown in the hurdle of table 30,31 sample No.155.
[table 30]
| Example No. | Sample No. | La | Co | n | x | | z |
| Embodiment | |||||||
| 15 | 151 | The preceding interpolation | The preceding interpolation | 5.80 | 0.10 | 0.34 | 0.24 |
| Embodiment 16 | 152 | The preceding interpolation | Front/rear interpolation | 5.74 | 0.10 | 0.34 | 0.12 |
| Embodiment 17 | 153 | The preceding interpolation | Add the back | 5.68 | 0.10 | 0.34 | 0 |
| Embodiment 18 | 154 | Front/rear interpolation | The preceding interpolation | 5.95 | 0.10 | 0.31 | 0.24 |
| Embodiment 19 | 155 | Front/rear interpolation | Add the back | 5.95 | 0.10 | 0.31 | 0 |
Table 30 is continuous
| Example No. | Sample No. | (1-x-y)/ (1-y) | y/x | x/z | y/ |
| Embodiment | |||||
| 15 | 151 | 0.85 | 3.4 | 0.42 | 1.42 |
| Embodiment 16 | 152 | 0.85 | 3.4 | 0.83 | 2.83 |
| Embodiment 17 | 153 | 0.85 | 3.4 | - | - |
| Embodiment 18 | 154 | 0.86 | 3.1 | 0.42 | 1.29 |
| Embodiment 19 | 155 | 0.86 | 3.1 | - | - |
[table 31]
| Example No. | Sample No. | a | b | c | d | n′ | x+b | y+c | z+ |
| Embodiment | |||||||||
| 15 | 151 | 0 | 0.115 | 0 | 0 | 5.20 | 0.215 | 0.34 | 0.24 |
| Embodiment 16 | 152 | 0 | 0.115 | 0 | 0.12 | 5.20 | 0.215 | 0.34 | 0.24 |
| Embodiment 17 | 153 | 0 | 0.115 | 0 | 0.24 | 5.20 | 0.215 | 0.34 | 0.24 |
| Embodiment 18 | 154 | 0 | 0.115 | 0.026 | 0 | 5.21 | 0.215 | 0.34 | 0.24 |
| Embodiment 19 | 155 | 0 | 0.115 | 0.026 | 0.24 | 5.32 | 0.215 | 0.34 | 0.24 |
Table 31 (continuing)
| Example No. | Sample No. | (1-x-y+a)/ (1-y+a+b) | (y+c) /(z+d) | (y+c)/x | x/(z+d) |
| | 151 | 0.72 | 1.42 | 3.4 | 0.42 |
| Embodiment 16 | 152 | 0.72 | 1.42 | 3.4 | 0.42 |
| Embodiment 17 | 153 | 0.72 | 1.42 | 3.4 | 0.42 |
| Embodiment 18 | 154 | 0.73 | 1.42 | 3.4 | 0.42 |
| Embodiment 19 | 155 | 0.73 | 1.42 | 3.4 | 0.42 |
Find according to Figure 16, embodiment 15 (La: preceding interpolation, preceding interpolation), embodiment 16 (La: preceding interpolation Co:, front/rear interpolation), embodiment 17 (La: preceding interpolation Co:, Co: afterwards add), embodiment 18 (La: front/rear interpolation, preceding interpolation) and embodiment 19 (La: front/rear interpolation Co:, Co: add the back) the anisotropic ferrite sintered magnet have magnetic characteristic more than the equal extent with the magnet of the embodiment 9,14 of table 27, have the higher magnetic characteristic of magnet in addition than the example in the past 7 of table 27.
The discussion of＜mishmetal class (R=La, Ce, Pr, Nd) raw material 〉
Use SrCO
3Powder, CaCO
3Powder, R material powder (with 2 kinds of mixing in the middle of La oxide powder, Ce oxide powder, Pr oxide powder and the Nd oxide powder), α-Fe
2O
3Powder and CoOOH powder carry out wet mixed and pre-burning and (in the atmosphere, 1523K), have made the pre-burning body of the basic composition of sample No.161～163 shown in the table 32.And, when described wet mixed, added the SiO of 0.2 mass parts with respect to mixture 100 mass parts
2Powder.Later on identical with embodiment 1, carried out that dry type coarse crushing, wet type micro mist are broken, shaping and sintering in the magnetic field.Measured the magnetic characteristic of room temperature of the anisotropic ferrite sintered magnet of gained.The results are shown in the figure line of sample No.161～163 of Figure 17.In addition, the basic composition of the pre-burning body of gained and sintered body is shown in the hurdle of sample No.161～163 of table 32 and 33.
[table 32]
| Example No. | Sample No. | R | n | x | | z |
| Embodiment | ||||||
| 20 | 161 | La50％+Ce50％ | 5.8 | 0.10 | 0.34 | 0.24 |
| 162 | La50％+Pr50％ | 5.8 | 0.10 | 0.34 | 0.24 | |
| 163 | La50％+Nd50％ | 5.8 | 0.10 | 0.34 | 0.24 | |
| Example 7 in the past | 113 | La100％ | 5.8 | 0 | 0.34 | 0.24 |
| Embodiment 9 | 115 | La100％ | 5.8 | 0.10 | 0.34 | 0.24 |
Table 32 is continuous
| Example No. | Sample No. | (1-x-y)/ (1-y) | y/x | x/z | y/ |
| Embodiment | |||||
| 20 | 161 | 0.85 | 3.4 | 0.42 | 1.4 |
| 162 | 0.85 | 3.4 | 0.42 | 1.4 | |
| 163 | 0.85 | 3.4 | 0.42 | 1.4 | |
| Example 7 in the past | 113 | 1.0 | - | 0 | 1.4 |
| Embodiment 9 | 115 | 0.85 | 3.4 | 0.42 | 1.4 |
[table 33]
| Example No. | Sample No. | a | b | c | d | n′ | x+b | y+c | z+ |
| Embodiment | |||||||||
| 20 | 161 | 0.035 | 0.084 | 0 | 0 | 5.18 | 0.184 | 0.34 | 0.24 |
| 162 | 0.035 | 0.084 | 0 | 0 | 5.18 | 0.184 | 0.34 | 0.24 | |
| 163 | 0.035 | 0.084 | 0 | 0 | 5.18 | 0.184 | 0.34 | 0.24 | |
| Example 7 in the past | 113 | 0.036 | 0.084 | 0 | 0 | 5.18 | 0.084 | 0.34 | 0.24 |
| Embodiment 9 | 115 | 0.035 | 0.084 | 0 | 0 | 5.18 | 0.184 | 0.34 | 0.24 |
Table 33 (continuing)
| Example No. | Sample No. | (1-x-y+a)/ (1-y+a+b) | (y+c) /(z+d) | (y+c)/x | x/(z+d) |
| | 161 | 0.76 | 1.42 | 3.40 | 0.42 |
| 162 | 0.76 | 1.42 | 3.40 | 0.42 | |
| 163 | 0.76 | 1.42 | 3.40 | 0.42 | |
| Example 7 in the past | 113 | 0.76 | 1.42 | - | 0 |
| Embodiment 9 | 115 | 0.76 | 1.42 | 3.40 | 0.42 |
Find that according to Figure 17 the magnetic characteristic of anisotropic ferrite sintered magnet (sample No.161～163) that must contain the embodiment 20 of La as R is than example (sample No.113) was higher in the past.
Embodiment 21
Sintering in the＜oxygen 〉
Slip after utilizing the micro mist identical with the material of made among embodiment 9, the sample No.115 broken has carried out being shaped in the magnetic field.The formed body of gained was distinguished sintering 2 hours under (partial pressure of oxygen 1.0atm), sintering temperature: 1483K, 1493K, 1498K and the 1503K in oxygen atmosphere.Measured the magnetic characteristic of room temperature of the anisotropic ferrite sintered magnet of gained.The result is represented with the figure line of the sample No.171 of Figure 18.In addition, the basic composition of the pre-burning body of gained and sintered body is shown in the hurdle of sample No.171 of table 34 and 35.
[table 34]
| Example No. | Sample No. | n | x | y | z | (1-x-y)/ (1-y) | y/x | x/z | y/z |
| Embodiment 21 | 171 | 5.8 | 0.10 | 0.34 | 0.24 | 0.85 | 3.4 | 0.42 | 1.4 |
| Example 7 in the past | 113 | 5.8 | 0 | 0.34 | 0.24 | 1.0 | - | 0 | 1.4 |
| Embodiment 9 | 115 | 5.8 | 0.10 | 0.34 | 0.24 | 0.85 | 3.4 | 0.42 | 1.4 |
[table 35]
| Example No. | Sample No. | a | b | c | d | n′ | x+b | y+c | z+d |
| Embodiment 21 | 171 | 0.035 | 0.084 | 0 | 0 | 5.18 | 0.184 | 0.34 | 0.24 |
| Example 7 in the past | 113 | 0.036 | 0.084 | 0 | 0 | 5.18 | 0.084 | 0.34 | 0.24 |
| Embodiment 9 | 115 | 0.035 | 0.084 | 0 | 0 | 5.18 | 0.184 | 0.34 | 0.24 |
Table 35 (continuing)
| Example No. | Sample No. | (1-x-y+a)/ (1-y+a+b) | (y+c) /(z+d) | (y+c)/x | x/(z+d) |
| Embodiment 21 | 171 | 0.76 | 1.42 | 3.40 | 0.42 |
| Example 7 in the past | 113 | 0.89 | 1.42 | - | 0 |
| Embodiment 9 | 115 | 0.76 | 1.42 | 3.40 | 0.42 |
According to Figure 18, in oxygen sintering the magnetic characteristic of anisotropic ferrite sintered magnet (sample No.171) of embodiment 21 than example 7 (sample No.113) was obviously higher in the past.
Each the pre-burning body of embodiment 1～21 and the representational sample of anisotropic ferrite sintered magnet have been carried out X-ray diffraction mensuration, found that all be that M is mutually single-phase.
＜utilizing with M is the anisotropic ferrite sintered magnet that the pre-burning system of principal phase is made mutually 〉
Use SrCO
3Powder, CaCO
3Powder, La hydroxide powder, α-Fe
2O
3Powder and CoOOH powder carry out wet mixed and pre-burning and (in the atmosphere, 1523K), have made the pre-burning body of the basic composition of the sample No.181 shown in the table 36.And, in the wet mixed operation before pre-burning, added the SiO of 0.2 mass parts with respect to mixture 100 mass parts
2Powder.Pre-burning body to gained has carried out X-ray diffraction mensuration, and the result has also seen α-Fe except M phase (principal phase)
2O
3Diffraction spectrogram.Later on identical with embodiment 1, carried out that dry type coarse crushing, wet type micro mist are broken, shaping and sintering in the magnetic field.Measured the magnetic characteristic of room temperature of the anisotropic ferrite sintered magnet of gained.The results are shown in the table 38.In addition, the basic composition of the pre-burning body of gained and sintered body is shown in the hurdle of sample No.181 of table 36 and 37.
[table 36]
| Example No. | Sample No. | n | x | y | z | (1-x-y)/ (1-y) | y/x | x/z | y/ |
| Embodiment | |||||||||
| 22 | 181 | 6.6 | 0.12 | 0.38 | 0.27 | 0.81 | 3.2 | 0.44 | 1.4 |
| Embodiment 9 | 115 | 5.8 | 0.10 | 0.34 | 0.24 | 0.85 | 3.4 | 0.42 | 1.4 |
[table 37]
| Example No. | Sample No. | a | b | c | d | n′ | x+b | y+c | z+ |
| Embodiment | |||||||||
| 22 | 181 | 0.175 | 0.094 | 0 | 0 | 5.20 | 0.214 | 0.38 | 0.27 |
| Embodiment 9 | 115 | 0.035 | 0.084 | 0 | 0 | 5.18 | 0.184 | 0.34 | 0.24 |
Table 37 (continuing)
| Example No. | Sample No. | (1-x-y+a)/ (1-y+a+b) | (y+c) /(z+d) | (y+c)/x | x/(z+d) |
| | 181 | 0.76 | 1.41 | 3.17 | 0.44 |
| Embodiment 9 | 115 | 0.76 | 1.42 | 3.40 | 0.42 |
[table 38]
| Example No. | Sample No. | Br (mT) | Hcj (kA/m) |
| | 181 | 431 | 389.1 |
| Embodiment 9 | 115 | 433 | 389.9 |
The result of X-ray diffraction shows that the anisotropic ferrite sintered magnet of embodiment 22 has M type ferrite structure.Find that according to table 38 utilizing with M is that the anisotropic ferrite sintered magnet of the embodiment 22 that makes of the pre-burning system of principal phase has the higher magnetic characteristic with the anisotropic ferrite sintered magnet equal extent of embodiment 9 mutually.
The assay value and the basic composition of sample of the main anisotropic ferrite sintered magnet of experiment carried out in table 39 expression.The assay value of anisotropic ferrite sintered magnet is that the total amount that constitutes metallic element is represented as 100 atom %.In addition, the basic composition utilization of anisotropic ferrite sintered magnet is with (Sr, Ba)
1-x '-y 'Ca
X 'La
Y 'Fe
2n '-z 'Co
Z 'O
19X ' during expression, y ', z ' and n ' expression.X ', y ', z ' and n ' respectively do for oneself Ca content, La content, Co content and the mol ratio of anisotropic ferrite sintered magnet.Added
*Sample be example or comparative example in the past.
[table 39]
Assay value of＜anisotropic ferrite sintered magnet (atom %) and basic composition 〉
| Sample No. | Ba | Sr | Ca | La | Fe | Mn | Co | Si | Al | Cr |
| 1 * | 0.07 | 5.76 | 0.65 | 2.38 | 88.00 | 0.42 | 2.06 | 0.61 | 0.04 | 0.00 |
| 2 | 0.06 | 4.98 | 1.45 | 2.38 | 88.01 | 0.42 | 2.06 | 0.61 | 0.04 | 0.00 |
| 3 | 0.05 | 4.19 | 2.24 | 2.38 | 88.01 | 0.42 | 2.06 | 0.61 | 0.04 | 0.00 |
| 4 | 0.04 | 3.41 | 3.03 | 2.38 | 88.02 | 0.42 | 2.06 | 0.60 | 0.04 | 0.00 |
| 5 * | 0.07 | 5.49 | 0.66 | 3.03 | 87.03 | 0.41 | 2.66 | 0.62 | 0.03 | 0.00 |
| 6 | 0.06 | 4.42 | 1.73 | 3.04 | 87.03 | 0.41 | 2.66 | 0.61 | 0.03 | 0.00 |
| 7 | 0.04 | 3.43 | 2.73 | 3.04 | 87.04 | 0.41 | 2.66 | 0.61 | 0.03 | 0.00 |
| 8 * | 0.03 | 2.36 | 3.81 | 3.04 | 87.05 | 0.41 | 2.66 | 0.60 | 0.03 | 0.00 |
| 9 * | 0.02 | 1.38 | 4.80 | 3.04 | 87.06 | 0.41 | 2.66 | 0.60 | 0.04 | 0.00 |
| 10 * | 0.07 | 5.29 | 1.44 | 2.06 | 88.01 | 0.42 | 2.06 | 0.61 | 0.04 | 0.00 |
| 11 | 0.06 | 4.98 | 1.45 | 2.38 | 88.01 | 0.42 | 2.06 | 0.61 | 0.04 | 0.00 |
| 12 | 0.06 | 4.66 | 1.45 | 2.70 | 88.00 | 0.42 | 2.06 | 0.61 | 0.04 | 0.00 |
| 13 | 0.06 | 4.35 | 1.45 | 3.02 | 88.00 | 0.42 | 2.06 | 0.61 | 0.04 | 0.00 |
| 14 | 0.05 | 4.04 | 1.45 | 3.33 | 88.00 | 0.42 | 2.06 | 0.61 | 0.04 | 0.00 |
| 15 | 0.05 | 3.72 | 1.45 | 3.65 | 87.99 | 0.42 | 2.06 | 0.62 | 0.04 | 0.00 |
| 16 * | 0.05 | 3.80 | 2.73 | 2.66 | 87.05 | 0.41 | 2.66 | 0.61 | 0.03 | 0.00 |
| 17 | 0.04 | 3.39 | 2.73 | 3.08 | 87.04 | 0.41 | 2.66 | 0.61 | 0.03 | 0.00 |
| 18 | 0.04 | 3.06 | 2.73 | 3.41 | 87.04 | 0.41 | 2.66 | 0.61 | 0.03 | 0.00 |
| 19 | 0.06 | 5.05 | 1.44 | 2.30 | 88.18 | 0.42 | 1.90 | 0.61 | 0.04 | 0.00 |
| 20 | 0.06 | 4.66 | 1.45 | 2.70 | 88.00 | 0.42 | 2.06 | 0.61 | 0.04 | 0.00 |
| 21 | 0.05 | 3.88 | 2.35 | 2.76 | 87.64 | 0.41 | 2.27 | 0.61 | 0.04 | 0.00 |
| 22 | 0.04 | 3.06 | 2.73 | 3.41 | 87.04 | 0.41 | 2.66 | 0.61 | 0.03 | 0.00 |
| 23 * | 0.08 | 6.09 | 0.65 | 1.86 | 88.69 | 0.42 | 1.55 | 0.61 | 0.04 | 0.01 |
| 24 * | 0.07 | 5.76 | 0.65 | 2.38 | 88.00 | 0.42 | 2.06 | 0.61 | 0.04 | 0.00 |
| 25 * | 0.07 | 5.45 | 0.66 | 3.08 | 87.03 | 0.41 | 2.66 | 0.62 | 0.03 | 0.00 |
| 26 * | 0.00 | 0.27 | 5.18 | 4.18 | 85.83 | 0.41 | 3.49 | 0.61 | 0.03 | 0.00 |
| 30 * | 0.03 | 2.62 | 3.82 | 2.38 | 88.03 | 0.42 | 2.06 | 0.60 | 0.04 | 0.00 |
| 31 * | 0.04 | 3.17 | 3.27 | 2.38 | 88.02 | 0.42 | 2.06 | 0.60 | 0.04 | 0.00 |
| 40 * | 0.06 | 4.52 | 0.66 | 3.52 | 87.99 | 0.42 | 2.19 | 0.62 | 0.04 | 0.00 |
| 65 * | 0.07 | 5.49 | 0.66 | 3.03 | 87.03 | 0.41 | 2.66 | 0.62 | 0.03 | 0.00 |
| 66 | 0.06 | 4.42 | 1.73 | 3.04 | 87.03 | 0.41 | 2.66 | 0.61 | 0.03 | 0.00 |
| 67 | 0.04 | 3.43 | 2.73 | 3.04 | 87.04 | 0.41 | 2.66 | 0.61 | 0.03 | 0.00 |
| 68 * | 0.03 | 2.36 | 3.81 | 3.04 | 87.05 | 0.41 | 2.66 | 0.60 | 0.03 | 0.00 |
| 69 * | 0.02 | 1.38 | 4.80 | 3.04 | 87.06 | 0.41 | 2.66 | 0.60 | 0.04 | 0.00 |
Table 39 (continuing)
| Sample No. | x’ | y’ | z’ | n’ |
| 1 * | 0.07 | 0.27 | 0.23 | 5.10 |
| 2 | 0.16 | 0.27 | 0.23 | 5.10 |
| 3 | 0.25 | 0.27 | 0.23 | 5.11 |
| 4 | 0.34 | 0.27 | 0.23 | 5.11 |
| 5 * | 0.07 | 0.33 | 0.29 | 4.87 |
| 6 | 0.19 | 0.33 | 0.29 | 4.88 |
| 7 | 0.30 | 0.33 | 0.29 | 4.88 |
| 8 * | 0.41 | 0.33 | 0.29 | 4.88 |
| 9 * | 0.52 | 0.33 | 0.29 | 4.88 |
| 10 * | 0.16 | 0.23 | 0.23 | 5.10 |
| 11 | 0.16 | 0.27 | 0.23 | 5.10 |
| 12 | 0.16 | 0.30 | 0.23 | 5.10 |
| 13 | 0.16 | 0.34 | 0.23 | 5.10 |
| 14 | 0.16 | 0.38 | 0.23 | 5.10 |
| 15 | 0.16 | 0.41 | 0.23 | 5.10 |
| 16 * | 0.30 | 0.29 | 0.29 | 4.88 |
| 17 | 0.30 | 0.33 | 0.29 | 4.88 |
| 18 | 0.30 | 0.37 | 0.29 | 4.88 |
| 19 | 0.16 | 0.26 | 0.21 | 5.11 |
| 20 | 0.16 | 0.30 | 0.23 | 5.10 |
| 21 | 0.26 | 0.31 | 0.25 | 5.00 |
| 22 | 0.30 | 0.37 | 0.29 | 4.88 |
| 23 * | 0.08 | 0.21 | 0.18 | 5.23 |
| 24 * | 0.07 | 0.27 | 0.23 | 5.10 |
| 25 * | 0.07 | 0.33 | 0.29 | 4.87 |
| 26 * | 0.54 | 0.43 | 0.36 | 4.66 |
| 30 * | 0.43 | 0.27 | 0.23 | 5.11 |
| 31 * | 0.37 | 0.27 | 0.23 | 5.11 |
| 40 * | 0.08 | 0.40 | 0.25 | 5.18 |
| 65 * | 0.07 | 0.33 | 0.29 | 4.87 |
| 66 | 0.19 | 0.33 | 0.29 | 4.88 |
| 67 | 0.30 | 0.33 | 0.29 | 4.88 |
| 68 * | 0.41 | 0.33 | 0.29 | 4.88 |
| 69 * | 0.52 | 0.33 | 0.29 | 4.88 |
Table 39 (continuing)
| Sample No. | Ba | Sr | Ca | La | Fe | Mn | Co | | Al | Cr | |
| 101 * | 0.08 | 6.14 | 0.65 | 1.88 | 88.63 | 0.42 | 1.56 | 0.61 | 0.04 | 0.00 | |
| 102 | 0.07 | 5.75 | 1.04 | 1.88 | 88.63 | 0.42 | 1.56 | 0.61 | 0.04 | 0.00 | |
| 103 | 0.07 | 5.36 | 1.43 | 1.88 | 88.63 | 0.42 | 1.56 | 0.61 | 0.04 | 0.01 | |
| 104 | 0.06 | 4.98 | 1.82 | 1.88 | 88.63 | 0.42 | 1.56 | 0.61 | 0.04 | 0.01 | |
| 105 * | 0.07 | 5.83 | 0.65 | 2.19 | 88.63 | 0.42 | 1.56 | 0.61 | 0.04 | 0.00 | |
| 106 | 0.07 | 5.44 | 1.04 | 2.19 | 88.63 | 0.42 | 1.56 | 0.61 | 0.04 | 0.00 | |
| 107 | 0.06 | 5.06 | 1.43 | 2.19 | 88.63 | 0.42 | 1.56 | 0.61 | 0.04 | 0.00 | |
| 108 | 0.06 | 4.67 | 1.82 | 2.19 | 88.64 | 0.42 | 1.56 | 0.61 | 0.04 | 0.00 | |
| 109 * | 0.07 | 5.75 | 0.65 | 2.27 | 88.32 | 0.42 | 1.88 | 0.61 | 0.04 | 0.00 | |
| 110 | 0.07 | 5.37 | 1.04 | 2.27 | 88.32 | 0.42 | 1.88 | 0.61 | 0.04 | 0.00 | |
| 111 | 0.06 | 4.98 | 1.43 | 2.27 | 88.32 | 0.42 | 1.88 | 0.61 | 0.04 | 0.00 | |
| 112 | 0.06 | 4.59 | 1.82 | 2.27 | 88.32 | 0.42 | 1.88 | 0.61 | 0.04 | 0.00 | |
| 113 * | 0.07 | 5.37 | 0.66 | 2.66 | 88.31 | 0.42 | 1.88 | 0.61 | 0.04 | 0.00 | |
| 114 | 0.06 | 4.98 | 1.04 | 2.66 | 88.31 | 0.42 | 1.88 | 0.61 | 0.04 | 0.00 | |
| 115 | 0.06 | 4.59 | 1.43 | 2.66 | 88.32 | 0.42 | 1.88 | 0.61 | 0.04 | 0.00 | |
| 116 | 0.05 | 4.21 | 1.82 | 2.66 | 88.32 | 0.42 | 1.88 | 0.61 | 0.04 | 0.00 | |
| 117 | 0.05 | 4.21 | 1.44 | 3.05 | 88.00 | 0.42 | 2.19 | 0.61 | 0.04 | 0.00 | |
| 118 | 0.05 | 3.82 | 1.82 | 3.05 | 88.01 | 0.42 | 2.19 | 0.61 | 0.04 | 0.00 | |
| 119 | 0.04 | 3.44 | 2.21 | 3.05 | 88.01 | 0.42 | 2.19 | 0.61 | 0.04 | 0.00 | |
| 120 | 0.05 | 3.75 | 1.44 | 3.52 | 88.00 | 0.42 | 2.19 | 0.61 | 0.04 | 0.00 | |
| 121 | 0.04 | 3.36 | 1.83 | 3.52 | 88.00 | 0.42 | 2.19 | 0.61 | 0.04 | 0.00 | |
| 122 | 0.04 | 2.97 | 2.22 | 3.52 | 88.00 | 0.42 | 2.19 | 0.61 | 0.04 | 0.00 | |
| 123 * | 0.08 | 6.45 | 0.65 | 1.64 | 88.56 | 0.42 | 1.57 | 0.60 | 0.04 | 0.00 | |
| 124 | 0.08 | 5.99 | 1.03 | 1.72 | 88.56 | 0.42 | 1.57 | 0.60 | 0.04 | 0.00 | |
| 125 | 0.07 | 5.53 | 1.04 | 2.19 | 88.24 | 0.42 | 1.88 | 0.61 | 0.04 | 0.00 | |
| 126 | 0.06 | 4.84 | 1.42 | 2.50 | 88.24 | 0.42 | 1.88 | 0.61 | 0.04 | 0.00 | |
| 127 | 0.08 | 5.98 | 1.04 | 1.64 | 88.71 | 0.42 | 1.48 | 0.61 | 0.04 | 0.00 | |
| 128 | 0.07 | 5.86 | 1.04 | 1.81 | 88.65 | 0.42 | 1.49 | 0.61 | 0.04 | 0.00 | |
| 129 * | 0.07 | 5.89 | 1.04 | 1.78 | 88.60 | 0.42 | 1.55 | 0.61 | 0.04 | 0.00 | |
| 130 * | 0.07 | 5.88 | 1.04 | 1.79 | 88.66 | 0.42 | 1.50 | 0.61 | 0.04 | 0.00 | |
| 131 * | 0.08 | 6.41 | 0.65 | 1.65 | 88.65 | 0.42 | 1.49 | 0.61 | 0.04 | 0.00 |
Table 39 (continuing)
| Sample No. | x’ | y’ | z’ | n’ |
| 101 * | 0.07 | 0.21 | 0.18 | 5.19 |
| 102 | 0.12 | 0.21 | 0.18 | 5.19 |
| 103 | 0.16 | 0.21 | 0.18 | 5.19 |
| 104 | 0.21 | 0.21 | 0.18 | 5.19 |
| 105 * | 0.07 | 0.25 | 0.18 | 5.18 |
| 106 | 0.12 | 0.25 | 0.18 | 5.19 |
| 107 | 0.16 | 0.25 | 0.18 | 5.19 |
| 108 | 0.21 | 0.25 | 0.18 | 5.19 |
| 109 * | 0.07 | 0.26 | 0.21 | 5.18 |
| 110 | 0.12 | 0.26 | 0.21 | 5.18 |
| 111 | 0.16 | 0.26 | 0.21 | 5.19 |
| 112 | 0.21 | 0.26 | 0.21 | 5.19 |
| 113 * | 0.07 | 0.30 | 0.21 | 5.18 |
| 114 | 0.12 | 0.30 | 0.21 | 5.18 |
| 115 | 0.16 | 0.30 | 0.21 | 5.18 |
| 116 | 0.21 | 0.30 | 0.21 | 5.19 |
| 117 | 0.16 | 0.35 | 0.25 | 5.18 |
| 118 | 0.21 | 0.35 | 0.25 | 5.18 |
| 119 | 0.25 | 0.35 | 0.25 | 5.19 |
| 120 | 0.16 | 0.40 | 0.25 | 5.18 |
| 121 | 0.21 | 0.40 | 0.25 | 5.18 |
| 122 | 0.25 | 0.40 | 0.25 | 5.18 |
| 123 * | 0.07 | 0.19 | 0.18 | 5.14 |
| 124 | 0.12 | 0.19 | 0.18 | 5.14 |
| 125 | 0.12 | 0.25 | 0.21 | 5.14 |
| 126 | 0.16 | 0.28 | 0.21 | 5.14 |
| 127 | 0.12 | 0.19 | 0.17 | 5.19 |
| 128 | 0.12 | 0.21 | 0.17 | 5.15 |
| 129 * | 0.12 | 0.20 | 0.18 | 5.16 |
| 130 * | 0.12 | 0.20 | 0.17 | 5.16 |
| 131 * | 0.07 | 0.19 | 0.17 | 5.15 |
Claims (9)
1. ferrite sintered magnet, it is characterized in that, be to have M type ferrite structure, with the A element that is made of Sr or Sr and Ba, as at least a of the rare earth element that contains Y and R element, Ca, Fe and the Co that must contain La is the ferrite sintered magnet of indispensable element, utilization is the operation manufacturing of oxidate magnetic material pulverizing, shaping and sintering, and the basic composition of described oxidate magnetic material is by following general formula (1):
A
1-x-yCa
xR
yFe
2n-zCo
zO
19(atom ratio) ... (1)
Expression, the basic composition of described ferrite sintered magnet are by following general formula (2):
A
1-x-y+aCa
X+bR
Y+cFe
2n-zCo
Z+dO
19(atom ratio) ... (2) expression, in described general formula (1) and (2), x, y, z and n represent amount and the mol ratio of Ca, R element and Co in the described oxidate magnetic material respectively, a, b, c and d are illustrated respectively in the amount of the A element, Ca, R element and the Co that add in the pulverizing process of described oxidate magnetic material, are to satisfy following condition respectively:
0.03≤x≤0.4
0.1≤y≤0.6
0≤z≤0.4
4≤n≤10
x+y＜1
0.03≤x+b≤0.4
0.1≤y+c≤0.6
0.1≤z+d≤0.4
0.50≤[(1-x-y+a)/(1-y+a+b)]≤0.97
1.1≤(y+c)/(z+d)≤1.8
1.0≤(y+c)/x≤20 reach
0.1 the numeral of≤x/ (z+d)≤1.2.
2. ferrite sintered magnet according to claim 1 is characterized in that, described oxidate magnetic material is a principal phase with M mutually.
3. ferrite sintered magnet according to claim 1 is characterized in that, described oxidate magnetic material is for being the pre-burning body of principal phase mutually with M.
4. according to any described ferrite sintered magnet in the claim 1～3, it is characterized in that, add in the mixed processes of full dose before pre-burning with R element and Co.
5. according to any described ferrite sintered magnet in the claim 1～3, it is characterized in that, add in the mixed processes of a part before pre-burning with the full dose of R element and Co, add in the pulverizing process of surplus after pre-burning with Co.
6. according to any described ferrite sintered magnet in the claim 1～3, it is characterized in that, add in the mixed processes of full dose before pre-burning with the R element, add in the pulverizing process of full dose after pre-burning with Co.
7. according to any described ferrite sintered magnet in the claim 1～3, it is characterized in that, add in the mixed processes of full dose before pre-burning with the part of R element and Co, add in the pulverizing process of surplus after pre-burning with R.
8. according to any described ferrite sintered magnet in the claim 1～3, it is characterized in that, add in the mixed processes of a part before pre-burning with R element and Co, add in the pulverizing process of surplus after pre-burning with R element and Co.
9. according to any described ferrite sintered magnet in the claim 1～3, it is characterized in that, add in the mixed processes of a part before pre-burning with the R element, add in the pulverizing process of full dose after pre-burning with the surplus of R element and Co.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210447375.3A CN102945718B (en) | 2003-09-12 | 2004-09-13 | Ferrite sintered magnet |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003321988 | 2003-09-12 | ||
| JP321988/2003 | 2003-09-12 | ||
| JP058098/2004 | 2004-03-02 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210447375.3A Division CN102945718B (en) | 2003-09-12 | 2004-09-13 | Ferrite sintered magnet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1849675A true CN1849675A (en) | 2006-10-18 |
Family
ID=37078454
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200480026243 Pending CN1849675A (en) | 2003-09-12 | 2004-09-13 | Ferrite sintered magnet |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1849675A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102496438A (en) * | 2007-03-01 | 2012-06-13 | Tdk株式会社 | Ferrite sintered magnet |
| CN102666431A (en) * | 2010-03-17 | 2012-09-12 | Tdk株式会社 | Ferrite magnetic material, ferrite magnet, ferrite sintered magnet |
| CN102976735A (en) * | 2012-11-19 | 2013-03-20 | 宁波科星材料科技有限公司 | Magnetic material used for manufacturing built-in antenna and preparation method thereof |
| CN103011795A (en) * | 2012-11-19 | 2013-04-03 | 宁波科星材料科技有限公司 | Preparation method of magnetic material for preparing built-in antenna |
| CN111533550A (en) * | 2019-02-07 | 2020-08-14 | Tdk株式会社 | Ferrite sintered magnet |
| CN114249591A (en) * | 2020-09-24 | 2022-03-29 | 日立金属株式会社 | Ferrite pre-sintered body and method for producing same |
| CN117185796A (en) * | 2023-09-25 | 2023-12-08 | 浙江凯文磁钢有限公司 | Method for manufacturing M-type permanent magnetic ferrite material by binary formula |
-
2004
- 2004-09-13 CN CN 200480026243 patent/CN1849675A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102496438A (en) * | 2007-03-01 | 2012-06-13 | Tdk株式会社 | Ferrite sintered magnet |
| CN101542646B (en) * | 2007-03-01 | 2012-07-11 | Tdk株式会社 | Ferrite sintered magnet |
| CN102496438B (en) * | 2007-03-01 | 2015-04-01 | Tdk株式会社 | Ferrite sintered magnet |
| CN102666431A (en) * | 2010-03-17 | 2012-09-12 | Tdk株式会社 | Ferrite magnetic material, ferrite magnet, ferrite sintered magnet |
| CN102666431B (en) * | 2010-03-17 | 2015-06-17 | Tdk株式会社 | Ferrite magnetic material, ferrite magnet, ferrite sintered magnet |
| CN102976735A (en) * | 2012-11-19 | 2013-03-20 | 宁波科星材料科技有限公司 | Magnetic material used for manufacturing built-in antenna and preparation method thereof |
| CN103011795A (en) * | 2012-11-19 | 2013-04-03 | 宁波科星材料科技有限公司 | Preparation method of magnetic material for preparing built-in antenna |
| CN111533550A (en) * | 2019-02-07 | 2020-08-14 | Tdk株式会社 | Ferrite sintered magnet |
| US11440848B2 (en) | 2019-02-07 | 2022-09-13 | Tdk Corporation | Ferrite sintered magnet |
| CN114249591A (en) * | 2020-09-24 | 2022-03-29 | 日立金属株式会社 | Ferrite pre-sintered body and method for producing same |
| CN117185796A (en) * | 2023-09-25 | 2023-12-08 | 浙江凯文磁钢有限公司 | Method for manufacturing M-type permanent magnetic ferrite material by binary formula |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1265402C (en) | Ferrimagnet producing method and motor | |
| CN1155022C (en) | Oxide magnetic material, ferrite particles, sintered magnet, bonded magnet, magnetic recording medium and motor | |
| CN1093311C (en) | Rare earth-iron-nitrogen magnet alloy | |
| CN1012477B (en) | Rare earth-iron-boron magnet powder and process of producing same | |
| CN1239578A (en) | Magnet powder, sintered magnet, method of mfg. these materials, bonded magnet, motor, and magnetic recording medium | |
| CN1242424C (en) | Permanent magnet and R-TM-B series permanent magnet | |
| CN1271647C (en) | Magnet powder, method for producing sintered magnet, and product thereof | |
| CN85109738A (en) | Rare earth alloy powder and preparation technology thereof | |
| CN1411006A (en) | Rare earth bonded magnet and rare earth iron boron type magnet alloy | |
| CN1036554C (en) | Permanent magnet with good thermal stability | |
| CN1545567A (en) | Sputtering target, transparent conductive film, and method for producing same | |
| CN1120506C (en) | Nd-Fe-B permanent magnet | |
| CN1200907C (en) | Piezoelectric porcelain and method for preparation thereof and piezoelectric element | |
| CN1273675A (en) | Hxagonal ferrite magnet | |
| CN1111799A (en) | Magnetic powder, permanent magnet produced therefrom and process for producing them | |
| CN101056729A (en) | Method for producing soft magnetic metal powder coated with Mg-containing oxide film and method for producing composite soft magnetic material from the powder | |
| CN1767087A (en) | Ferrite magnetic material and process for producing the same | |
| CN1182545C (en) | Method for mfg piezoelectric ceramics composition and piezoelectric ceramics element, and piezoelectric laminated sinter | |
| CN1455938A (en) | Permanent magnet and method for preparation thereof | |
| CN1557005A (en) | R-T-B based rare earth element permanent magnet | |
| CN1029272C (en) | Method of manufacturing oxide superconductor, and method of manufacturing composite oxide powder which is precursor of oxide superconductor | |
| CN1300047C (en) | Method for making ferrite magnets | |
| CN1849675A (en) | Ferrite sintered magnet | |
| CN1012235B (en) | Process for manufacturing permanent magnet | |
| CN1873844A (en) | Method for producing ferrite magnet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: HITACHI METAL CO., LTD. Free format text: FORMER OWNER: SHINO MAGNITIC MATEERIAL CO., LTD. Effective date: 20070831 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20070831 Address after: Tokyo, Japan, Japan Applicant after: Hitachi Metals Co., Ltd. Address before: Osaka Japan Applicant before: Neomax Co., Ltd. |
|
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20061018 |