CN102010194B - Magneto-plumbite type permanent magnetic ferrite and manufacturing method thereof - Google Patents
Magneto-plumbite type permanent magnetic ferrite and manufacturing method thereof Download PDFInfo
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Abstract
The invention discloses a magneto-plumbite type permanent magnetic ferrite and a manufacturing method thereof, and belongs to the field of permanent magnetic ferrites. The main components of the permanent magnetic ferrite are shown in (CaO)x.(R2O3)y.(Fe2O3)n, wherein R is at least one element of La, Nd and Pr and certainly comprises La; and a compound additive SrmMpBzOm+p+2z serving as an auxiliary component is added, wherein M is at least one element of Co, Zn, Ni, Mn and Cu and certainly comprises Co, and x, y, n, m, p and z in the formula represent the molar ratio of the added main metal elements respectively. An optimized process design is adopted, and the autonomously developed compound additive SrmMpBzOm+p+2z is added, so that the liquid phase sintering of a product is facilitated, the grain structure of the product is improved, and even if low-cost iron scale is taken as a main raw material, a magnet with high magnetic performance is manufactured under the condition of small substitution amount of the cobalt element.
Description
Technical field:
A kind of permanent-magnet ferrite of the present invention and manufacture method thereof relate to the permanent-magnet ferrite field, and be particularly relevant with permanent-magnet ferrite.
Background technology:
Permanent-magnet ferrite material is a kind of functional materials that produces magnetic field, and high-performance permanent-magnet ferrite plays an important role in the industries such as electronic industry, information industry, motorcycle, power tool, automotive industry.A large amount of Ferrite Materials that use are the Sr ferrite (SrFe with M type magnetoplumbite type at present
12O
19), the final magnetic property of its magnet generally is by remanent magnetism Br, HCJ H
CJWeigh.In recent years, when the high efficiency of the miniaturization of electric motor of automobile, lightweight, device for electric machine requires permanent-magnet ferrite to keep high remanent magnetism Br, has stronger anti-demagnetization capability, i.e. the HCJ H of material
CJRequire high.Known to La
3+, Co
2+Replace the formula technique of Sr-Fe Deng part, improved significantly the magnetic property of permanent-magnet ferrite material.
This class Sr ferrite take the carbonate of ferric oxide and Sr as main raw material, forms with the powder metallurgic method manufacturing usually.At first, ferric oxide, Strontium carbonate powder etc. is mixed, just single-step solid phase reaction occurs by pre-burning, obtain Preburning material piece (or pellet), with after its coarse breaking take water as medium, it carefully is crushed to median size is that (be 200910095297.3 Chinese patent such as application number, the granularity of ball milling is controlled at below the 0.65 μ m 0.5～0.7 μ m after its pre-burning; Application number is that 20068004983.2 Chinese patent is mentioned in embodiment, and the granularity of ball milling is controlled at below the 0.55 μ m after its pre-burning; Application number is 200610169039.1 Chinese patent, and Slurry Granularity is preferably 0.1～0.4 μ m before its moulding below 0.8 μ m, is preferably 0.1～0.2 μ m again).In crushing process, be the growth of control crystal grain, add SiO
2, SrCO
3, CaCO
3Deng additive, for improving the H of material
CJ, add Al
2O
3, Cr
2O
3Deng additive.Then with slip moulding in magnetic field of milled, with the blank sintering of gained, wear into the shape of regulation, make the permanent-magnet ferrite magnet.
In above-mentioned manufacturing process, particulate median size in the slip that obtains through the wet type Crushing of Ultrafine is lower than 0.7 μ m, and during moulding, the time of draining obviously increases slip in magnetic field, shaping efficiency descends greatly, and this will cause the manufacturing cost of permanent-magnet ferrite magnet to increase.As to adopt median size be slip moulding in magnetic field more than the 0.7 μ m, and then shaping efficiency will obviously improve.But its magnetic property can reduce with the increase of the mean particle size of slip.
Application number is 200910095297.3 Chinese patent application, the granularity of slip is controlled at below the 0.65 μ m before its moulding, and the moulding difficulty is large, especially when the domestic mould molding not high enough with the making precision, that tolerance clearance is larger, run easily material, product percent of pass is low.Therefore adopted the way (solids content of its slip is 70% among the embodiment) that reduces water content.But water content is low, will reduce the orientation degree of slip, affects the magnetic property of material.In addition, at the general formula A of its main formula
1-x-yCa
xR
yFe
2n-zM
zO
19In, preferred as it, A all is Sr, and R all is La, and M all is Co; As preferably, its 0.6≤y≤1.0,0.6≤z≤1.0.Namely preferred as it, the replacement amount of its expensive Elements C o is higher, thereby its production cost is higher.
Application number is 20068004983.2 Chinese patent, and in embodiment 12,13 optimum formula, the replacement amount of its expensive Elements C o is higher.Be 99% ferric oxide, 1000 grams such as every input mass percent, need add Co content and be 74% cobalt oxide 33.82～38.65 grams, its production cost is higher.
In the academic paper of H.Yamamoto et al.IEEE Trans Maga MAG-15 (1979), mention a kind of Ca-La permanent-magnet ferrite, its chemical constitution is (CaOFe
2O
3)
100-X(La
2O
3)
X, when X=2～3, found to have M type magnetoplumbite type in this compound, when X=3, the magnetic property of material is obtained optimum value, and its optimum value is: Br=4100Gs, H
CB=2050 Oe, H
CJ=2100 Oe, its magnetic property is lower.
Summary of the invention:
The purpose of this invention is to provide a kind of permanent-magnet ferrite and manufacture method thereof, when the wet pressing pressing under magnetic field was provided, drainage effect was good, the permanent-magnet ferrite material that production cost is low, magnetic property is extremely excellent and the making method of magnet.
The objective of the invention is to be achieved through the following technical solutions:
Permanent-magnet ferrite of the present invention, its main composition is (Ca0)
X(R
2O
3)
Y(Fe
2O
3)
n, R is selected from La, Nd, and at least a element among the Pr, and necessarily contain La; As its minor component, added a kind of composite additive Sr
mM
pB
zO
M+p+2z, M is selected from Co, Zn, and Ni, Mn, at least a element among the Cu, and necessarily contain Co, and the x that relates in the composition formula, y, n, m, p, z represent respectively the adding proportion by each major metal element of mole number, wherein:
N is 4.5～7.0, and preferred n is 5.5～6.2,
X is that 0.2～0.5, y is 0.3～0.7, and x+y is 0.8～1.0,
M is that 0.1～2.0, p is that 0.001～3.0, z is 0.1～4.0, and m/z=0.5～3.0.
In the present invention, mainly adopted La
3+(its ionic radius is 0.122nm), Ca
2+(its ionic radius is 0.09nm) replaces the Sr in the magnetoplumbite type jointly
2+(its ionic radius is 0.113nm) realizes.If La
3+Or Ca
2+Replace separately Sr
2+, will be difficult to obtain high magnetic property.This be since the principle that occur to replace between the ion to be that ionic radius differs the smaller the better, on the other hand, La
3+In the forming process of magnetoplumbite type, can crystal grain thinning, thus improve the H of material
CJAnd Ca
2+In the forming process of magnetoplumbite type, can improve the density of material, this is favourable to the Br that improves material.
According to research, Sr (BO
2)
2Melt gradually at 900 ℃ to 1100 ℃, form a kind of non-oxidizable flux, it can be to Al
2O
3Or the high sample fusion and decomposition of iron-holder, this decomposition temperature is near 1100 ℃, and the present invention has developed a kind of composite additive Sr
mM
pB
zO
M+p+2z, M is selected from Co, Zn, Ni, Mn, at least a element among the Cu, and necessarily containing Co, is that 0.1～2.0, p is 0.001～3.0 by m, z is 0.1～4.0, and m/z=0.5～3.0, calculates to contain Sr, M, the addition of the compound of the elements such as B, and accurately weighing, its addition means can take a kind of mode of the following stated to carry out:
A, the mix stages before pre-burning directly add, pre-sinter process is: the raw material that mixes that obtains with mixed processes 1240 ℃～1320 ℃ insulations 0.1～10 hour in air of will preparing burden, be preferably, in air, be incubated 0.1～4 hour under 800 ℃～1100 ℃, then continue to be warmed up to 1260 ℃～1300 ℃ insulations 0.1～5 hour;
B, the shredding stage after pre-burning directly add, sintering process is: formed body is incubated 2～4 hours under 150 ℃～400 ℃, fully remove moisture and organism in the formed body, then in air, be incubated 0.1～3 hour under 1170～1250 ℃, be preferably: formed body is incubated 2～4 hours in air under 150 ℃～400 ℃, insulation is 0.1～4 hour under 800 ℃～1100 ℃, then is warmed up to 1170～1250 ℃ of lower insulations 0.1～3 hour;
C, employing dry method or wet method will contain Sr, M, the compound of the elements such as B is even, in 800 ℃～1100 ℃ lower insulations 0.1～4 hour, is preferably 1～3 hour in air, then to be broken to mean particle size be 1～3 μ m to fine powder, and the mix stages before pre-burning or the shredding stage after the pre-burning add.
Additive Sr
mM
pB
zO
M+p+2zPromoted the liquid phase sintering of product, improved the crystalline-granular texture of product, the section sem analysis of gained magnet shows, its crystal is the hexagonal plate structure, and radius-thickness ratio is 3.0～3.5, and average crystal grain diameter is 0.5～2.5 μ m, be preferably 1.0～2.0 μ m, grain size is relatively even, and structural arrangement is tight, and void content is 0.2～0.6% in the magnet.
The present invention has improved the H of permanent-magnet ferrite material by this most effective approach of magnetocrystalline anisotropy that improves material
CJ, because the crystal anisotropy constant K of M type permanent-magnet ferrite
1＞0, the present invention makes crystal anisotropy constant K by adding the additive that contains in right amount the Co element
1＞0, thus reach the H that improves permanent-magnet ferrite material
CJPurpose; Simultaneously, the composite additive Sr that develops by the present invention
mM
VB
UO
ZForm add, improved the utilization ratio of noble metal Co element, reduced the consumption of Co element, on the other hand, reduce the residual impurity of grain boundaries, improved permanent-magnet ferrite material and magnet crystal grain microtexture, thereby improved significantly the magnetic property of material.Even use mass percent: TFe 〉=73%, FeO 〉=38%, MnO≤0.2%, SiO
2The iron scale with low cost of≤0.1%, S≤0.1% is in the situation of main raw material, also can obtain the extremely excellent magnet of magnetic property.
As ferrite magnet of the present invention, can add Si as its minor component.Interpolation its objective is in suitable sintering range as the Si of minor component, the grain-size of control product.The SiO that adds as the Si composition
2, its addition is 0.01%～1.0%, is preferably 0.1%～0.7%.
As ferrite magnet of the present invention, can also add Cr, Al is as its minor component, and the purpose of interpolation is to improve H
CJ, but the amount of adding is too much, and Br descends.Interpolation is as the Cr of minor component Cr
2O
3, its addition is 0.01%～3%.Interpolation is as the Al of minor component Al
2O
3, its addition is 0.01%～3%.
According to research, the height of permanent-magnet ferrite material magnetic property directly depends on the pattern of ferrite particle.And the subject matter in existing broken stage of fine powder is: on the one hand, because the High Temperature Pre imitation frosted glass of permanent-magnet ferrite is difficult to grind, the grinding plant of noticeable wear and will pollute ferrite ferrite from the extraneous element of grinding medium, this is disadvantageous to its magnetic property; On the other hand, because primary particle is difficult to separately, grinding will cause increasing of the following particle of 0.2 μ m for a long time, these particles are when moulding, part is pumped in drainage procedure, this particle that is not pumped of part will bring adverse influence to the orientation in magnetic field, perhaps have the possibility that small-particle reunites again, the possibility that occurs recrystallize in the double sintering process etc.The method of the mean particle size of slip had reduced the broken time of fine powder when the present invention had adopted suitable raising fine powder broken, had improved the efficient of moulding.
The preparation of permanent-magnet ferrite of the present invention realizes by following process steps:
(1) composite additive Sr of the present invention
mM
pB
zO
M+p+2zPreparation and adding technology---M is selected from Co, Zn, Ni, Mn, at least a element among the Cu, and necessarily contain Co, be that 0.1～2.0, p is that 0.001～3.0, z is 0.1～4.0 by m, and m/z=0.5～3.0, calculating contains Sr, M, the addition of the compound of the elements such as B, and accurately weighing, its addition means can take a kind of mode of the following stated to carry out:
1. the mix stages before pre-burning directly adds, pre-sinter process is: the raw material that mixes that obtains with mixed processes 1240 ℃～1320 ℃ insulations 0.1～10 hour in air of will preparing burden, be preferably: in air, be incubated 0.1～4 hour under 800 ℃～1120 ℃, be preferably 1～3 hour, then continue to be warmed up to 1260 ℃～1300 ℃ insulations 0.1～5 hour;
2. the shredding stage after pre-burning directly adds, sintering process is: formed body is incubated 2～4 hours under 150 ℃～400 ℃, fully remove moisture and organism in the formed body, then in air, be incubated 0.1～3 hour under 1170～1250 ℃, be preferably: formed body is incubated 2～4 hours in air under 150 ℃～400 ℃, insulation is 0.1～4 hour under 800 ℃～1120 ℃, is preferably 1～3 hour, then is warmed up to 1170～1250 ℃ of lower insulations 0.1～3 hour.
3. adopt dry method or wet method, to contain Sr, M, the compound of the elements such as B is even, in air, under 800 ℃～1120 ℃, be incubated 0.1～4 hour, be preferably 1～3 hour, then to be broken to mean particle size be 1～3 μ m to fine powder, mix stages before pre-burning or the shredding stage after the pre-burning add, pre-sinter process is: the raw material that mixes that obtains with mixed processes 1240 ℃～1320 ℃ insulations 0.1～10 hour in air of will preparing burden, sintering process is: formed body 150 ℃～400 ℃ lower insulations 2～4 hours, is fully removed moisture and organism in the formed body, then be incubated 0.1～3 hour under 1170～1250 ℃ in air.
(2) batching and mix: according to composition formula (Ca0)
X(R
2O
3)
Y(Fe
2O
3)
n, x wherein, y, n represent respectively the adding proportion by each major metal element of mole number, calculate the addition of each main composition raw material, the compound that then will contain each element is by the accurate weighing of the amount of calculating and mix.Mixing between each main raw material, the whole or main composition raw material of part adds all or partly and maybe wouldn't add the minor component raw material by the adding of quality proportioning, and employing dry method or wet-mixed are even, and main composition raw material and the minor component raw material of surplus add after pre-burning.
When adopting wet-mixed, its mixing time is 1～6 hour, by the Fe of the present invention as main raw material
2O
3, can adopt purity is more than 99.0%, more preferably the Fe more than 99.3%
2O
3, granularity should at 0.3～3.0 μ m, be preferably 0.3～1.0 μ m; Also can use mass percent: TFe 〉=73%, FeO 〉=38%, MnO≤0.2%, SiO
2The iron scale of≤0.1%, S≤0.1% is 0.3～3.0 μ m through being ground to mean particle size, is preferably after 1.0～2.0 μ m, and the powder in 850 ℃～900 ℃ oxidation kiln behind oxide treatment 1.5～2h is as the Fe of its principal constituent
2O
3
(3) pre-burning: the raw material that mixes that obtains with mixed processes 1240 ℃～1320 ℃ insulations 0.1～10 hour in air of will preparing burden are preferably in the air 1260 ℃～1300 ℃ insulations 0.1～5 hour;
(4) pulverize: behind gained Preburning material dry type coarse breaking to 1 μ m～4 μ m, 1 μ m～2 μ m preferably, then the quality proportioning of calculating by step (1) adds surplus master composition, and surplus or whole minor components, and it is broken to carry out fine powder with wet method, is to obtain industrial production and high magnetic property, the mean particle size of its slip is controlled at 0.2 μ m～1.5 μ m, if the mean particle size of slip is below 0.2 μ m, product is when moulding, and its draining characteristics will significantly worsen; When sintering, the H of material abnormal grain! growth will appear,
CJReduce.If the mean particle size of slip is more than 1.5 μ m, then the ratio of ferrite multidomain grain increases, slip is under the forming magnetic field effect, the magnetic history of these big particles mainly is the displacement process of domain wall, this magnetic history is so that the saturation remanent flux of multidomain grain is significantly less than the particle of uniform magnetization, and this will cause the Br of material obviously to descend.On the other hand, multidomain grain the demagnetization process that domain wall moves can occur under the effect of externally-applied magnetic field, and this will reduce the H of material greatly
CJFine mean particle size preferably is controlled to be 0.7 μ m～1.2 μ m; Be particularly preferably 0.75 μ m～0.85 μ m; For further improving the orientation degree of slip, can add an amount of known dispersion agent such as calglucon, Sorbitol Powder etc. and realize;
(5) moulding: the water content of above-mentioned steps gained slip is controlled at 28%～45%, preferably is controlled at 36%～40%, then at the action of a magnetic field compacted under, the magnetic field of magnetizing during moulding should be more than 10000Oe, preferably more than 15000Oe;
(6) sintering: formed body 150 ℃～400 ℃ lower insulations 2～4 hours, is fully removed moisture and organism in the formed body, then in air, be incubated 0.1～3 hour under 1170～1250 ℃, can obtain the extremely excellent magnet of magnetic property.
Permanent-magnet ferrite magnet of the present invention during sintering, under the room temperature (20 ℃), has the Br of 4200～4600Gs, the H of 5000～5200 Oe under air conditions
CJ, and 80% above squareness ratio (H
k/ H
CJ), particularly can have simultaneously the Br of 4300～4500Gs, the H of 5000～5200 Oe
CJ
The present invention compared with prior art has following advantage:
By being (Ca0) to principal constituent
X(R
2O
3)
Y(Fe
2O
3)
nFerrite Material and magnet, the mix stages before the pre-burning or the shredding stage after the pre-burning add Sr by aforementioned technique
mM
pB
zO
M+p+2z, promoted the liquid phase sintering of product, improved the crystalline-granular texture of product, even using mass percent: TFe 〉=73%, FeO 〉=38%, MnO≤0.2%, SiO
2The iron scale with low cost of≤0.1%, S≤0.1% is in the situation of main raw material, also can obtain the extremely excellent magnet of magnetic property.By the optimization design of prescription, especially at main formula principal constituent (Ca0)
X(R
2O
3)
Y(Fe
2O
3)
n, working as x=0.4, y=0.55, n are 5.9; As its minor component, the Sr of interpolation
mM
pB
zO
M+p+2z, work as m=0.9, p=2.7, z=0.3, and Sr
mM
pB
zO
M+p+2zAddition when being 2.3%, use mass percent: TFe 〉=73%, FeO 〉=38%, MnO≤0.2%, SiO
2The iron scale with low cost of≤0.1%, S≤0.1% is main raw material, can obtain Br=4421Gs, H
CJThe high magnetic characteristics permanent-magnet ferrite of=5101Oe.
In addition, the method for the mean particle size of slip had reduced the broken time of fine powder when the present invention had adopted suitable raising fine powder broken, had improved the efficient of moulding.
Description of drawings
Fig. 1 adds minor component Sr
mM
pB
zO
M+p+2zAfter, principal constituent is (Ca0)
X(R
2O
3)
Y(Fe
2O
3)
nMagnet SEM photo;
Fig. 2 presses Sr
mM
pB
zO
M+p+2zBatching is not heat-treated it, and principal constituent is (Ca0)
X(R
2O
3)
Y(Fe
2O
3)
nThe time, the SEM photo of gained magnet under common process;
The SEM photo of the existing technique gained magnet of the high replacement amount of the expensive Elements C o of Fig. 3;
When Fig. 4 mol ratio n changes in 4.7～7.0 scopes, the comparison diagram of magnetism of material energy.
Fig. 5 Sr
mM
pB
zO
M+p+2zAddition when changing, on the graph of a relation that affects of permanent-magnet ferrite magnetic property;
Fig. 6 Sr
mM
pB
zO
M+p+2zThermal treatment process on the graph of a relation that affects of permanent-magnet ferrite magnetic property;
Fig. 7 x+y is that 0.95, n is 5.9 o'clock, and the value of x is on the figure that affects of magnetism of material energy in the main formula;
Fig. 8 x+y is that 0.95, n is 5.9 o'clock, and the value of y is on the figure that affects of magnetism of material energy in the main formula;
Fig. 9 x is that 0.4, n is 5.9 o'clock, and the value of x+y is on the impact of magnetism of material energy.
Embodiment
Now with accompanying drawing the technology of the present invention feature is further described in conjunction with the embodiments,
With iron scale (mass percent: TFe 〉=73%, FeO 〉=38%, MnO≤0.2%, SiO
2≤ 0.1%, S≤0.1%), through being ground to after mean particle size is 1.5 μ m, the powder of oxide treatment after 1.5 hours is as the Fe of its principal constituent in 880 ℃ oxidation kiln
2O
3, other prepares massfraction is SrCO more than 98%
3Powder is the CaCO more than 98.5%
3Powder is the La more than 99%
2O
3The cobalt oxide powder more than 72% that powder, Co massfraction are; Minor component Sr
mM
pB
zO
M+p+2zPreparation: get m=0.9, p=2.7, z=0.3 adopts dry method or wet method that it is mixed, in 950 ℃ of lower insulations 2 hours, then fine powder was broken to the powder that mean particle size is 1.5 μ m in air.
To the principal constituent of material, (Ca0)
X(R
2O
3)
Y(Fe
2O
3)
n, x=0.4 wherein, y=0.55, n 5.9 calculate the addition of each main raw material.And be 2.3% to take by weighing Sr by the massfraction of Preburning material to be generated
mM
pB
zO
M+p+2z, each raw material of wet-mixed.Its mixing time is 4 hours.Then, with each raw material stoving that mixes, in air, be incubated 2 hours under 1295 ℃.With gained Preburning material dry type coarse breaking to 2 μ m.Get this crushed material 1000 grams and massfraction and be respectively 1% CaCO
3, 0.4% SiO
2, known dispersion agent calglucon 0.5%, and be 1: 12: 1.5 ratio in the mass ratio of material, ball, water, it is broken to carry out fine powder in the ball mill (cleaning up) that will expect, steel ball (cleaning up), water drops into φ 220 * 220.Measuring its mean particle size with WLP-208 is 0.80 μ m.The water content of gained slip is controlled at 38%, and then at the action of a magnetic field compacted under, the magnetic field of magnetizing during moulding is 12000 Oe, and forming pressure is 5.5Mpa, and the diameter of formed body is φ 30mm, highly is 13mm, and the water content of formed body is 13%.150 ℃～400 ℃ lower slowly intensifications, the heating-up time is 3 hours, fully removes the moisture in the formed body with this formed body, and then 1225 ℃ of lower insulations obtained sintered magnet in 1 hour in air.The microstructure of this magnet as shown in Figure 1.Magnet section sem analysis shows that its crystal is structure in the form of sheets, and radius-thickness ratio is that 3.0～3.5 crystal grain is 85%, and average crystal grain diameter is 1.5 μ m, and grain size is relatively even, and structural arrangement is tight, and void content is 0.4% in the magnet.
Carry out testing under the NIM-2000 permanent magnet material magnetic property detection system of Beijing metering institute manufacturing after the fine grinding with the upper and lower surface rubbing of this sintered magnet and with 135 purpose polishing wheels, its magnetic property sees Table 1.
Minor component Sr as material
mM
pB
zO
M+p+2z, the broken stage of the fine powder after pre-burning adds, and all the other are with embodiment 1, and the magnetic property of obtained sample sees Table 1.
Minor component Sr as material
mM
pB
zO
M+p+2z, the mix stages before pre-burning directly adds, and is incubated 2 hours under 950 ℃ in air, then is warmed up to 1295 ℃ of lower insulations 2 hours.All the other are with embodiment 1, and the magnetic property of obtained sample sees Table 1.
Minor component Sr as material
mM
pB
zO
M+p+2z, the shredding stage after pre-burning directly adds, and this formed body is slowly heated up under 150 ℃～400 ℃, heating-up time is 3 hours, fully remove the moisture in the formed body, then be warmed up to 950 ℃ of lower insulations 2 hours, 1225 ℃ of lower insulations obtained sintered magnet in 1 hour in air afterwards.All the other are with embodiment 1, and the magnetic property of obtained sample sees Table 1.
Comparative Examples 1
Minor component Sr as material
mM
pB
zO
M+p+2zRatio in embodiment 1 is calculated and weighing, it is not heat-treated, and the mix stages before pre-burning directly adds, all the other are with embodiment 1, the microstructure of obtained sample as shown in Figure 2, magnet section sem analysis shows that its crystal is structure in the form of sheets, radius-thickness ratio is that 1.8～2.8 crystal grain is 68%, the part has to surpass closes on the above large crystal grain existence of crystal grain twice, and structural arrangement is owed closely, and void content is 1.4% in the magnet.Its magnetic property is as shown in table 1.
Comparative Examples 2
Minor component Sr as material
mM
pB
zO
M+p+2z, calculate and weighing in the ratio of embodiment 1, it not to be heat-treated, the broken stage of the fine powder after pre-burning directly adds, and all the other are with embodiment 1, and the magnetic property of obtained sample sees Table 1.
Comparative Examples 3
Press Ca
0.38La
0.54Sr
0.09Fe
10Co
0.36O
19Calculate the addition of each main raw material, 1350 ℃ of lower pre-burnings are 3 hours in the air, add massfraction when fine powder is broken and be 1.4% CaCO
3, be 0.58% SiO
2Gained formed body 1220 ℃ of lower sintering 1 hour in air, all the other are with embodiment 1, the microstructure of the magnet that obtains as shown in Figure 2, magnet section sem analysis shows that its crystal is structure in the form of sheets, radius-thickness ratio is that 1.8～2.8 crystal grain is 75%, the part has the molten material to exist, and structural arrangement is owed closely, and void content is 0.9% in the magnet.Its magnetic property is as shown in table 1.
Table 1, material minor component Sr
mM
pB
zO
M+p+2zThe contrast technological experiment
To the principal constituent of material, (Ca0)
X(R
2O
3)
Y(Fe
2O
3)
n, x=0.4 wherein, y=0.55, mol ratio n changes in 4.7～7.0 scopes, and all the other are with embodiment 1, and the magnetic property of obtained sample is as shown in Figure 3.Data among Fig. 3 show that when n changed, when especially changing, as main raw material, the mean particle size of slip was near the 0.80 μ m when fine powder was broken with iron scale in 5.5～6.2 scopes in 4.7～7.0 scopes, when the Br of magnet surpasses 4400Gs, and its H
CJStill can reach more than 5000 Oe, this existing technique is difficult to realize.
Embodiment 6
To the principal constituent of material, (Ca0)
X(R
2O
3)
Y(Fe
2O
3)
n, x=0.4 wherein, y=0.55, n 5.9 calculate the addition of each main raw material.Material minor component Sr
mM
pB
zO
M+p+2zAddition in 0.1～6% scope, change, all the other are with embodiment 1, the magnetic property of obtained sample as shown in Figure 5.Data among Fig. 5 show, as material minor component Sr
mM
pB
zO
M+p+2zAddition when in 0.1%～6% scope, changing, when especially in 1.5%～4.0% scope, changing, do main raw material with iron scale, the mean particle size of slip was near the 0.80 μ m when fine powder was broken, when the Br of magnet surpasses 4400Gs, its H
CJStill can reach more than 5000 Oe, this existing technique is difficult to realize.
At the minor component Sr for preparing material
mM
pB
zO
M+p+2zThe time, its thermal treatment temp changes, and all the other are with embodiment 1, and the magnetic property of obtained sample is as shown in Figure 6.Data among Fig. 6 show, as material minor component Sr
mM
pB
zO
M+p+2zThermal treatment temp when 800 ℃～1100 ℃ lower variations, be when changing in the scope in 1.5～3 hours in soaking time especially, do main raw material with iron scale, the mean particle size of slip was near the 0.80 μ m when fine powder was broken, when the Br of magnet surpasses 4400Gs, its H
CJStill can reach more than 5000 Oe, this existing technique is difficult to realize.
Embodiment 8
To the principal constituent of material, (Ca0)
x(R
2O
3)
y(Fe
2O
3)
n, x is 0.2～0.5, and x+y is that 0.95, n is the addition of 5.9 each main raw material of calculating.All the other are with embodiment 1, and the magnetic property of obtained sample as shown in Figure 7.Data among Fig. 7 show, when x+y is that 0.95, n is 5.9 o'clock, x in 0.2～0.5 scope, the H of the sample that obtains
CJ Reach 4900 Oe when above, Br still can remain on more than the 4400Gs.
Embodiment 9
To the principal constituent of material, (Ca0)
x(R
2O
3)
y(Fe
2O
3)
n, y is 0.3～0.7, and x+y is that 0.95, n is the addition of 5.9 each main raw material of calculating.All the other are with embodiment 1, and the magnetic property of obtained sample as shown in Figure 8.Data among Fig. 8 show, when x+y is that 0.95, n is 5.9 o'clock, y is 0.3～0.7, and the magnetic property of the sample that obtains increases the H of material with the value of y
CJIncrease, Br slightly descends.And H
CJReach 4900 Oe when above, Br still can remain on more than the 4400Gs.
Embodiment 10
To the principal constituent of material, (Ca0)
x(R
2O
3)
y(Fe
2O
3)
n, x is 0.4, and x+y is that 0.7～1.1, n is 5.9 o'clock, calculates the addition of each main raw material.All the other are with embodiment 1, and the magnetic property of obtained sample as shown in Figure 9.Data among Fig. 9 show, when x+y 0.8 when following, the H of material
CJObviously descend, but that its Br changes is not obvious, when x+y 1.0 when above, the Br of material obviously descends, but its H
CJChange not obvious.
Although the present invention has been made detailed explanation and described some specific embodiments, embodiment is illustrating technical scheme of the present invention just.Understanding to the present invention program is not limited to embodiment.
Claims (10)
1. Magnetoplumbate-type permanent magnetic ferrite, its principal constituent is (CaO)
x(R
2O
3)
y(Fe
2O
3)
n, wherein, R is selected from La, Nd, and at least a element among the Pr, and necessarily contain La; Also add Sr
mM
pB
zO
M+p+2zAs minor component, wherein, M is selected from Co, Zn, and Ni, Mn, at least a element among the Cu, and necessarily contain Co; The addition of described minor component is 0.1%～6% of Magnetoplumbate-type permanent magnetic ferrite quality, the x that relates in the above-mentioned composition formula, and y, n, m, p, z represent respectively the adding proportion by each element of mole number, wherein:
N is 4.5～7.0,
X is that 0.2～0.5, y is 0.3～0.7, and x+y is 0.8～1.0,
M is that 0.1～2.0, p is that 0.001～3.0, z is 0.1～4.0, and m/z=0.5～3.0.
2. Magnetoplumbate-type permanent magnetic ferrite as claimed in claim 1, it is characterized in that: the addition of described minor component is 1.5%～4.0% of Magnetoplumbate-type permanent magnetic ferrite quality.
3. Magnetoplumbate-type permanent magnetic ferrite as claimed in claim 1, it is characterized in that: described minor component also contains the Si composition, the SiO that adds as the Si composition
2, its addition is 0.01%～1.0% of Magnetoplumbate-type permanent magnetic ferrite quality.
4. Magnetoplumbate-type permanent magnetic ferrite as claimed in claim 1, it is characterized in that: described minor component also contains Cr and Al composition, adds the Cr as minor component Cr
2O
3, its addition is 0.01%～3% of Magnetoplumbate-type permanent magnetic ferrite quality, adds the Al as minor component Al
2O
3, its addition is 0.01%～3% of Magnetoplumbate-type permanent magnetic ferrite quality.
5. Magnetoplumbate-type permanent magnetic ferrite as claimed in claim 1 is characterized in that: as principal constituent (CaO)
x(R
2O
3)
y(Fe
2O
3)
n, x=0.4, y=0.55, n are 5.9; As its minor component, the Sr of interpolation
mM
pB
zO
M+p+2z, m=0.9, p=2.7, z=0.3, and Sr
mM
pB
zO
M+p+2zAddition be 2.3%.
6. the preparation method of the described Magnetoplumbate-type permanent magnetic ferrite of any one among the claim 1-5, its preparation process is:
(1) batching and mix: according to composition formula (CaO)
x(R
2O
3)
y(Fe
2O
3)
nX wherein, y, n represents respectively the adding proportion by each major metal element of mole number, calculate the addition of each main composition raw material, add all or part of main composition raw material by the quality proportioning, select secondary composition raw material and addition, add part and maybe wouldn't add the minor component raw material, adopt dry method or wet-mixed even;
(2) pre-burning: the raw material that mixes that obtains with mixed processes 1240 ℃～1320 ℃ insulations 0.1～10 hour in air of will preparing burden;
(3) pulverize: behind gained Preburning material dry type coarse breaking to 1 μ m～4 μ m, the quality proportioning of then calculating by step (1) adds surplus master composition, and surplus or whole minor component, and is broken to 0.2 μ m～1.5 μ m with the wet method fine powder;
(4) moulding: the water content of above-mentioned steps gained slip is controlled at 28%～45%, and then at the action of a magnetic field compacted under, the magnetic field of magnetizing during moulding should be more than 10000Oe;
(5) sintering: formed body 150 ℃～400 ℃ lower insulations 2～4 hours, is fully removed moisture and organism in the formed body, then in air, be incubated 0.1～3 hour under 1170～1250 ℃, can obtain magnet.
7. the preparation method of Magnetoplumbate-type permanent magnetic ferrite as claimed in claim 6 is characterized in that: the water content of slip is controlled at 36%～40% in the step (4).
8. the preparation method of Magnetoplumbate-type permanent magnetic ferrite as claimed in claim 6 is characterized in that: with Sr
mM
pB
zO
M+p+2zBy Sr claimed in claim 1, M, the adding proportion of B element is calculated the addition of each composition raw material, and accurately weighing, and its addition means takes wherein a kind of mode of the following stated to carry out:
A, the mix stages before pre-burning directly add, and pre-sinter process is: be incubated 0.1～4 hour under 800 ℃～1100 ℃ in air, then continue to be warmed up to 1260 ℃～1300 ℃ insulations 0.1～5 hour;
B, the shredding stage after pre-burning directly add, and sintering process is: with formed body in air in 150 ℃～400 ℃ lower insulations 2～4 hours, then 800 ℃～1100 ℃ lower insulations 0.1～4 hour are warmed up to 1170～1250 ℃ of lower insulations 0.1～3 hour;
C,Adopt dry method or wet method, with contain respectively the Sr element compound, contain the M element compound, contain the B element compound even, in air, under 800 ℃～1100 ℃, be incubated 0.1～4 hour, then to be broken to mean particle size be 1～3 μ m to fine powder, mix stages before pre-burning or the shredding stage after the pre-burning add, and pre-burning and sintering process are undertaken by (2) step in the claim 7 and (5) step.
9. the preparation method of Magnetoplumbate-type permanent magnetic ferrite according to claim 6 is characterized in that: wherein, and as the raw material Fe of main composition
2O
3, employing purity is the Fe more than 99.0%
2O
3, its mean particle size is at 0.3～3.0 μ m.
10. the preparation method of Magnetoplumbate-type permanent magnetic ferrite according to claim 6 is characterized in that: adopt mass percent: TFe 〉=73%, FeO 〉=38%, MnO≤0.2%, SiO
2The iron scale of≤0.1%, S≤0.1%, through being ground to after mean particle size is 0.3～3.0 μ m, the powder in 850 ℃～900 ℃ oxidation kiln behind oxide treatment 1.5～2h is as the raw material Fe of principal constituent
2O
3
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| CN102832005A (en) * | 2012-09-13 | 2012-12-19 | 北矿磁材科技股份有限公司 | Environment-friendly halogen-free ferrite composite magnetic material |
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| EP3734622A4 (en) | 2017-12-27 | 2021-01-13 | Fujifilm Corporation | Particles of magnetoplumbite-type hexagonal ferrite and method for manufacturing same, and radio wave absorber |
| CN111439995B (en) * | 2019-01-17 | 2022-04-26 | 四川京都龙泰科技有限公司 | High-performance Co-free hexagonal permanent magnetic ferrite material and preparation method thereof |
| CN111573794A (en) * | 2020-05-28 | 2020-08-25 | 中国林业科学研究院林产化学工业研究所 | Ferrite permanent magnetic material and preparation method and application thereof |
| CN114195498A (en) * | 2021-12-14 | 2022-03-18 | 湖南航天磁电有限责任公司 | Low-cost permanent magnet barium ferrite and preparation method thereof |
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