High magnetic permeability ferrite in manganese zinc series of frequency response characteristic excellence and preparation method thereof
Technical field
The present invention relates to a kind of Mn-Zn based ferrite, relate in particular to ferrite in manganese zinc series of a kind of high magnetic permeability with excellent frequency characteristic and preparation method thereof.
Background technology
Soft magnetic ferrite is used as the magnetic core of inductive elements such as transformer, inducer, wave filter, high-performance power switch because of its high magnetic permeability, its demand is with increasing.Fast development along with the information industry technology, the manufacturing technology of electronics is updated and is upgraded, require the switch of electronics and calculating, processing speed more and more faster, but soft magnetic ferrite exists magnetic hysteresis loss, eddy-current loss and residual loss etc. after the match at alternating electromagnetism, and under high frequency, above-mentioned loss is aggravation all the more also, causes the magnetic core temperature to raise rapidly, and serviceability sharply descends.Traditional Mn-Zn based ferrite, when operating frequency is 10KHz under the room temperature condition, initial permeability still can reach 10000, but when operating frequency is brought up to 200KHz, the test initial permeability has only 5000, so traditional product can only be used under the occasion that operating frequency is lower than 100KHz, can not be adapted to the needs of the electronics of develop rapidly.
For solving above-mentioned similar problem, it is that 03115906.0 Chinese patent application file discloses a kind of manganese-zinc power soft ferrite material powder and preparation method thereof, Fe in the soft magnetic ferrite material powder that the patent No. is arranged
2O
3Be 58-79wt%, Mn
3O
4: 15-30wt%, ZnO:5-15wt%, auxiliary material (comprises SiO
2, CaCO
3, V
2O
5, Nb
2O
5): 0-7wt%, total amount satisfies 100%.Major ingredient and auxiliary material are made manganese-zinc power soft ferrite material powder by mixing, pre-burning, coarse reduction, sand milling, five operations of mist projection granulating, it is said that its finish mix powder power consumption is lower, saturation induction density Bs height, and superior performance, with low cost.
The patent No. that also has similarly is that 02150733.3 Chinese patent application file also discloses a kind of high frequency close grain soft magnetic ferrimagnetics material and production technique thereof, it is that main raw material is made by ferric oxide, zinc oxide and manganese oxide, the average grain size that it is characterized in that described soft magnetic ferrite is 3-5 μ m, and each component in the weight percentage ranges of oxide compound is: Fe
2O
3: 50-57%; ZnO:0-13%; MnO:30-50%; All the other are doping composition M; Its processing step that adopts is: batching, ball milling, vibration, pre-burning, sand milling, granulation, moulding, sintering, mill processing and packing, it is said: its technology is fit to industrialized mass production, the characteristics that production cost is low, process stabilizing, product have the magnetic permeability height, power loss is little, reach the technical indicator of high-frequency low-consumption power Ferrite Material PC50, thereby provide advantageous conditions for miniaturization, the chip type of realizing electron device.
Similarly, also having publication number is that the Japanese patent application file of JP2002118014 also discloses a kind of high frequency, high resistance Mn-Zn ferrite, and the proportioning of three kinds of major ingredients that it is taked and content are compared with common proportioning, are in comparatively special scope, are specially Fe
2O
3: 45.0~50.0mol%, ZnO:7.0~15.0mol%, MnO:35.0~48.0mol%.
Summary of the invention
The technical purpose that the present invention will reach is that a kind of high magnetic permeability ferrite in manganese zinc series and manufacture method thereof that all has on very wide operating frequency range than the frequency response characteristic excellence of high initial permeability will be provided.
For this reason, technical solution of the present invention is a kind of high magnetic permeability ferrite in manganese zinc series of frequency response characteristic excellence, and this ferrite comprises principal constituent and ancillary component, and principal constituent comprises ferric oxide, zinc oxide and manganese oxide, and principal constituent is as follows in the content of standard substance separately, Fe
2O
3: 51.0~53.0mol%, ZnO:21.0~23.0mol%, MnO: surplus; Described ancillary component comprises molybdenum oxide, bismuth oxide compound, calcium oxide and niobium oxide, described relatively principal constituent total amount, these ancillary components in standard substance separately content as follows respectively, MoO
3: 0.02~0.07wt%, Bi
2O
3: 0.01~0.06wt%, CaO:0.005~0.04wt%, Nb
2O
5: 0.005~0.04wt%.Ferrite in manganese zinc series of the present invention equal content of this major ingredient in the existing ferrite on the content of principal constituent zinc oxide, the ancillary component prescription that cooperates corresponding characteristic, make it to form more suitable microtexture, be more conducive between ferritic crystal boundary, produce resistive formation, reduce the wastage, on very wide operating frequency range, all improved ferritic initial permeability.
Characteristics in conjunction with principal constituent of the present invention, ancillary component of the present invention further comprise barium oxide, Si oxide, Zirconium oxide, titanium oxide wherein one or more, described relatively principal constituent total amount, these ancillary components are as follows in the content of its standard substance, V
2O
5: 0~0.04wt%, SiO
2: 0~0.02wt%, ZrO
2: 0~0.03wt%, TiO
2: 0~0.025wt%.V
2O
5Preferred content 0.005wt%~0.025wt%.
The content of described each ancillary component is its amount and follow-up addition sum in described principal constituent raw material.
Because above-mentioned prescription, ferritic magnetic permeability of the present invention is not less than 10000 and have the low specific loss factor when 10KHz, be not less than 8000 when 200KHz.Thereby improved the magnetic permeability of ferrite at high band.
Correspondingly, technical solution of the present invention is a kind of manufacture method of high magnetic permeability ferrite in manganese zinc series of aforesaid frequency response characteristic excellence, and this method comprises the steps: A) with the main raw material Fe of corresponding each principal constituent
2O
3, Mn
3O
4, ZnO mix to hold concurrently grinds, dry, pre-burning, obtains the main raw material powder through pre-burning; B) will through the main raw material powder of pre-burning with the auxiliary material of corresponding each ancillary component and tackiness agent mix hold concurrently grind, drying, obtain 80~300 microns dried particles; C) dried particles is suppressed on press obtained formed body, at 1300~1450 ℃ of sintering temperatures, sintering obtains described one-tenth type ferrite under the inflated with nitrogen atmosphere with formed body.
As the preferred embodiment of the inventive method, among the described step B of the present invention, described relatively principal constituent total amount, described tackiness agent is the carbon chain polymer of hydroxyl, the adding proportion of described tackiness agent is 0.4~1.0% (wt);
In conjunction with the domestic equipment present situation, among the described steps A of the inventive method, the B, described drying process is to adopt spray method; Among the described step C, the preferred temperature of described sintering process is 1350~1450 ℃, and soaking time is 4~10 hours, and described sintering process is to adopt pushed bat kiln stoking method or adopt top-hat kiln batch sintering process.
The invention will be further described below in conjunction with specific embodiment.
Embodiment
Embodiment series 1
With the Japanese NKK SH of company model Fe
3O
452.3mol%, (the raw material form is Mn to 25.7mol%MnO
3O
4), capital, Shanghai ZnO 22mol% adds as main component, adds ancillary component MoO
3(0.04~0.06wt), Bi
2O
3(0.030~0.05wt), add other ancillary components CaCO
3(0.01~0.03wt), V
2O
5(0.01~0.025wt), Nb
2O
5(one or more in 0.01~0.03wt) add the different auxiliary furtherance and get sample number into spectrum 1~10.
With above composition mixed after, carry out the secondary spraying for behind the spherical particle by spraying, pre-burning (calcined temperature is 850 ± 50 ℃), described relatively principal constituent total amount adding 0.6% (wt) adhesive polyethylene alcohol, the annular products of compression moulding H22mm * 14mm * 8mm, obtain 120 of formed bodys, with formed body at 1380~1420 ℃, kept 5~8 hours, carry out sintering, in the atmosphere of balance gas dividing potential drop, cool off then, each numbering is got 10 calculating mean values, at 23 ± 2 ℃, under the test condition of U=0.05V, record the table 1 that the results are shown in of this sample.
Table 1
Sample number into spectrum |
μ
i (10KHz)
|
μ
i (100KHz)
|
μ
i (200KHz)
|
Specific loss factor t an δ/μ
i×10
-6 (10KHz)
|
1 |
10125 |
10001 |
9025 |
2.83 |
2 |
10202 |
10025 |
9007 |
2.84 |
3 |
10542 |
9856 |
9023 |
2.76 |
4 |
10554 |
9978 |
9021 |
2.86 |
5 |
10124 |
9858 |
9008 |
2.68 |
6 |
11161 |
11103 |
9153 |
2.58 |
7 |
10212 |
9568 |
9132 |
2.64 |
8 |
9987 |
9824 |
9121 |
2.19 |
9 |
11250 |
9987 |
9014 |
2.54 |
10 |
10005 |
9684 |
9013 |
2.87 |
TDK H5C2 |
10000±25% |
There is not explanation |
There is not explanation |
<7 |
Embodiment series 2
With the Japanese NKK SH of company model Fe
3O
452mol%, (the raw material form is Mn to 26.4mol%MnO
3O
4), capital, Shanghai ZnO 21.6mol% adds as main component, adds ancillary component MoO
3(0.04~0.06wt%), Bi
2O
3(0.03~0.05wt%), add other ancillary components CaCO
3(0.01~0.05wt%), V
2O
5(0.01~0.04wt%), SiO
2(0.004~0.02wt%), ZrO
2(0~0.025wt%) and TiO
2(one or more in 0~0.025wt%) add the different auxiliary furtherance and get sample number into spectrum 1~10.
With above composition mixed after, carry out the secondary spraying for behind the spherical particle by spraying, pre-burning (calcined temperature is 850~920 ℃), described relatively principal constituent total amount adding 0.9% (wt) adhesive polyethylene alcohol, the annular products of compression moulding H22mm * 14mm * 8mm, obtain 120 of formed bodys, with formed body at 1380~1420 ℃, kept 5~8 hours, carry out sintering, in the atmosphere of balance gas dividing potential drop, cool off then, each numbering is got 10 calculating mean values, the results are shown in shown in the table 2 (test condition: 23 ± 2 ℃, U=0.05V).
Table 2
Sample number into spectrum |
μ
i (10KHz)
|
μ
i (100KHz)
|
μ
i (200KHz)
|
Specific loss factor t an δ/μ
i×10
-6 (10KHz)
|
1 |
10569 |
10354 |
9325 |
1.92 |
2 |
10230 |
10120 |
9020 |
2.25 |
3 |
11045 |
11010 |
9213 |
2.15 |
4 |
10540 |
10421 |
9051 |
2.21 |
5 |
10115 |
10121 |
9308 |
2.03 |
6 |
11151 |
10953 |
9053 |
2.28 |
7 |
10012 |
10052 |
9432 |
1.94 |
8 |
10057 |
10065 |
9243 |
2.16 |
9 |
10851 |
10865 |
9024 |
2.35 |
10 |
10132 |
10210 |
9245 |
2.29 |
TDK H5C2 |
10000±25% |
There is not explanation |
There is not explanation |
<7 |
By table 1 and table 2 as seen, the FERRITE CORE of present embodiment series 1,2 has the low specific loss factor, and magnetic permeability is not less than 10000 substantially when 10KHz, be not less than 8000 when 200KHz.