CN104098326A - Low-temperature-coefficient high-impedance high-magnetic-permeability manganese zinc ferrite material and preparation method thereof - Google Patents

Abstract

The invention discloses low-temperature-coefficient high-impedance high-magnetic-permeability manganese zinc ferrite material and a preparation method thereof, and belongs to the technical field of ferrite material preparation. The material comprises the components as follows: main components and at least two additives, wherein the main components comprise the following ingredients: 52.0 to 54.0 mol% of Fe2O3, 19.0 to 24.0 mol% of ZnO, 0.01 to 0.05 mol% of NiO, and the balance of MnO; the additives comprises the following ingredients: 0.01 to 0.08 wt% of CaCO3, 0.01 to 0.10 wt% of MoO3, 0.01 to 0.08 wt% of nano TiO2, 0.01 to 0.04 wt% of Bi2O3, 0.005 to 0.02 wt% of SiO2, 0.01 to 0.12 wt% of V2O5, 0.005 to 0.04 wt% of Nb2O5 and 0.005 to 0.04 wt% of B2O3. According to the invention, the material is uniform in size, obvious in grain boundary, and fewer in gas pores.

Description

Low-temperature coefficient high resistance High Initial Permeability MnZn Ferrite Materials and preparation method

Technical field

The invention belongs to Ferrite Material preparing technical field, particularly MnZn ferrite material with high magnetic conductivity of a kind of low-temperature coefficient, high resistance, frequency response characteristic excellence and preparation method thereof.

Background technology

Along with the develop rapidly of information technology, complete electronic set system is towards miniaturization, lightweight future development, this MnZn Ferrite Material that just requires to be applied to wherein has high magnetic permeability and high saturated magnetic induction, simultaneously, for fear of the puzzlement of various electromagnetic interference in environment, require various device to have very strong anti-electromagnetic interference (EMI) ability, this just requires the material that is applied to these devices to have high impedance characteristic to possess good anti-EMI performance; Meanwhile, because the complexity of surrounding environment changes, all kinds of devices also must meet envrionment temperature characteristic requirements, and this MnZn Ferrite Material that just requires to be applied in device possesses lesser temps coefficient, and magnetic permeability (inductance) varies with temperature insensitive; In addition, the switch of electronics and calculating, processing speed are more and more faster, certainly will cause being applied to height wherein leads MnZn FERRITE CORE magnetic permeability (inductance) under high frequency and is the trend of decay gradually, have a strong impact on the reliability of equipment and device, for this reason, the height that has an excellent frequency characteristic is led MnZn Ferrite Material becomes the key material of key of restriction device steady operation.

In recent years, famous magnetic materials production company and research and development institution all take much count of the research and development of MnZn ferrite material with high magnetic conductivity, for example T46 of EPCOS company (magnetic permeability μ both at home and abroad _i: 10kHz, 12000,200kHz, 8000; Curie temperature T _c:>=130 DEG C; 25～55 DEG C of relative temperature coefficient α _f:-0.6 × 10 ^-6), 3E6 (the magnetic permeability μ of FERROXCUBE company _i: 10kHz, 12000,200kHz, 9500; Curie temperature T _c:>=130 DEG C), MQ10T (the magnetic permeability μ of HITACHI company _i: 10kHz, 10000,200kHz, 9000; Curie temperature T _c:>=120 DEG C; 20～60 DEG C of relative temperature coefficient α _f: 1 × 10 ^-6), K10000 (the magnetic permeability μ of KASCHKE company _i: 10kHz, 10000,200kHz, 8500; Curie temperature T _c:>=125 DEG C; 25～70 DEG C of relative temperature coefficient α _f: 1 × 10 ^-6), SM-100 (the magnetic permeability μ of Samwha company of Korea S _i: 10kHz, 10000,200kHz, 10000; Curie temperature T _c:>=120 DEG C; 20～60 DEG C of relative temperature coefficient α _f: 1 × 10 ^-6), H5C4 (the magnetic permeability μ of TDK company _i: 10kHz, 12000,200kHz, 10000; Curie temperature T _c:>=120 DEG C; 20～60 DEG C of relative temperature coefficient α _f: 1 × 10 ^-6), 2H15 (the magnetic permeability μ of FDK company _i: 10kHz, 15000,200kHz, 6000; Curie temperature T _c:>=100 DEG C; 20～70 DEG C of relative temperature coefficient α _f: 1 × 10 ^-6), R15K (the magnetic permeability μ of Dong Ci company _i: 10kHz, 13000,200kHz, 11000; Curie temperature T _c: 105 DEG C of >; 20～80 DEG C of relative temperature coefficient α _f: 1 × 10 ^-6), HS123 (the magnetic permeability μ of Guangdong elegance and talent new and high technology company limited _i: 10kHz, 12000,200kHz, 10000; Curie temperature T _c:>=120 DEG C).From above-mentioned MnZn ferrite material with high magnetic conductivity, development and the development of this respect paid special attention in the commercial city of each large production both at home and abroad, material all has the fundamental characteristics of high magnetic permeability, only considers parameter of high magnetic permeability or two parameters, realizes than being easier to.The H5C5 magnetic permeability μ when the 10kHz announcing as TDK company _ican reach 30000, the rear μ but frequency raises _ifast-descending, and 110 DEG C of Curie temperature less thaies; Patent (CN200810060242.4) has been announced high magnetic conductivity soft-magnetic ferrite material and manufacture method thereof, its 10kHz and 100kHz magnetic permeability reach respectively 18000 and 14000, also>=125 DEG C of Curie temperature, the requirement of high magnetic permeability and high-curie temperature be can extraordinaryly meet, but impedance characteristic, magnetic permeability temperature profile and the permeability frequency characteristics of material in its result, do not provided; Patent (CN200710071536.2) has been announced a kind of high magnetic permeability MnZn ferrite and preparation method thereof, when its 10kHz, magnetic permeability is 10000, impedance within the scope of 100kHz～2MHz is 1.0～30k Ω, but permeability frequency characteristics and temperature profile thereof are not provided; Patent (CN201010224543.3) has been announced magnetic core that wide-temperature high-permeability Mn-Zn soft magnetic ferrite material makes with it and preparation method thereof, but in its result, does not provide impedance characteristic and the permeability frequency characteristics of material; Patent (CN201110230616.4) has been announced a kind of manufacture method of broad-band high-conductive manganese-zinc ferrite magnetic core, its frequency magnetic permeability below 100kHz can reach 13000, and necessary impedance characteristic, magnetic permeability temperature profile, permeability frequency characteristics result is not provided.

In sum, researching and developing a kind of MnZn Ferrite Material that has high magnetic permeability, high resistance, low-temperature coefficient and frequency response characteristic excellence concurrently certainly will become the focus that following research and development institution and company competitively chase, and it has important engineering background and marketable value.

Summary of the invention

The object of this invention is to provide MnZn ferrite material with high magnetic conductivity of a kind of low-temperature coefficient, high resistance, frequency response characteristic excellence and preparation method thereof.

Technical problem solved by the invention is, a kind of MnZn Ferrite Material and preparation method are provided, and its material has high magnetic permeability (μ _i: 13000), high-curie temperature (T _c:>=125 DEG C), low-temperature coefficient (α _f: < 0.5 × 10 ^-6/ DEG C), high resistance (Z:1.8k Ω～2.5k Ω) and excellent frequency stability (μ _i: 10kHz, 13000,200kHz, 12000).

The technical scheme that the present invention solve the technical problem employing is that low-temperature coefficient high resistance High Initial Permeability MnZn Ferrite Materials, comprises following component:

Principal constituent: Fe ₂o ₃: 52.0～54.0mol%, ZnO:19.0～24.0mol%, NiO:0.01～0.05mol%, surplus is MnO;

Also comprise at least two kinds in following additives: 0.01～0.08wt%CaCO ₃, 0.01～0.10wt%MoO ₃, 0.01～0.08wt% nano-TiO ₂, 0.01～0.04wt%Bi ₂o ₃, 0.005～0.02wt%SiO ₂, 0.01～0.12wt%V ₂o ₅, 0.005～0.04wt%Nb ₂o ₅with 0.005～0.04wt%B ₂o ₃.

The present invention also provides the preparation method of low-temperature coefficient high resistance High Initial Permeability MnZn Ferrite Materials, comprises the following steps:

1. formula:

Choose 52.0～54.0mol%Fe ₂o ₃, 19.0～24.0mol%ZnO, 0.01～0.05mol%NiO, all the other are MnO (Mn ₃o ₄as starting material)

2. a ball milling

To in ball mill, mix with material loading powder 1～3 hour time;

3. pre-burning

Step 2 gained ball milling material is dried, and pre-burning 1～4 hour in 850～950 DEG C of stoves;

4. doping

Step 3 gained material powder is added by weight to two or more combinations of following doping agent: 0.01～0.08wt%CaCO ₃, 0.01～0.10wt%MoO ₃, 0.01～0.08wt% nano-TiO ₂, 0.01～0.04wt%Bi ₂o ₃, 0.005～0.02wt%SiO ₂, 0.01～0.12wt%V ₂o ₅, 0.005～0.04wt%Nb ₂o ₅with 0.005～0.04wt%B ₂o ₃.

5. secondary ball milling

The Preburning material that adds impurity is put into ball mill, add the deionized water that pan feeding weighs 1.6 times, ball milling 1～4 hour, makes the mean particle size of Preburning material at 1.0 ± 0.1 μ m;

6. moulding

Step 5 gained material powder is added to 8～12wt% organic binder bond by weight, mix, after granulation, on press, granular powder is pressed into blank;

7. sintering

Step 6 gained blank is placed in to sintering in atmosphere sintering furnace, at 1000～1370 DEG C of temperature sections, volume ratio O ₂/ N ₂=1/999, at 1370～1420 DEG C of temperature sections, O ₂/ N ₂=4/96, be incubated 5～8 hours; Carry out balanced atmosphere sintering at temperature descending section.

8. test:

Step 7 gained sample is carried out to electromagnetic performance test.

By the inductance L of same favour TH2828 LCR test set test sample, suitably adjust coiling both end voltage value U _sit is met: U _s=4.44NfA _eb, the initial permeability of sample is calculated according to following formula:

${\mathrm{\&mu;}}_i=\frac{L\&times;{10}^7}{2N^{2}h\ln D/d}---\left(1\right)$

The inductance that wherein L is sample, N is number of turns, and h is thickness of sample, and D is sample external diameter, and d is sample internal diameter, f is test frequency, A _efor the net sectional area of sample.Test condition is: f=10kHz, B≤0.25mT.Draw μ in conjunction with temperature control box _i-T graphic representation, uses epitaxial method to determine Curie temperature T _c.

The test condition of sample frequency response characteristic is: f=10kHz～1MHz, B≤0.25mT.

Sample impedance is calculated according to following formula:

$Z=\mathrm{\&omega;}\frac{{\mathrm{\&mu;}}_0{N}^{2}h}{2\mathrm{\&pi;}}\ln \frac{r_2}{r_1}{\mathrm{\&mu;}}^{\&prime;\&prime;}+\mathrm{j\&omega;}\frac{{\mathrm{\&mu;}}_0{N}^{2}h}{2\mathrm{\&pi;}}\ln \frac{r_2}{r_1}{\mathrm{\&mu;}}^{\&prime;}---\left(2\right)$

Test condition is: f=10kHz～500kHz, B≤0.25mT.

Sample temperature coefficient calculates according to following formula:

${\mathrm{\&alpha;}}_{\mathrm{\&mu;}}=\frac{1}{\mathrm{\&mu;}}\&CenterDot;\frac{\&PartialD;\mathrm{\&mu;}}{\&PartialD;T}=\frac{{\mathrm{\&mu;}}_1-{\mathrm{\&mu;}}_{\mathrm{ref}}}{{\mathrm{\&mu;}}_{\mathrm{ref}}(T_1-T_{\mathrm{ref}})}---\left(3\right)$

Test condition is: f=10kHz, B≤0.25mT, T=20～80 DEG C.

With the magnetic hysteresis loop of IWATSU SY-8232B-H analyser test sample, test condition is: f=0.1kHz, H=1600A/m.

In sum, the present invention has the following advantages:

The present invention is by the formula, doping and the powder preparation technology that optimize, complete in conjunction with the MnZn Ferrite Material crystal grain that reasonably prepared by sintering environment, size uniform, and crystal boundary is obvious, and pore is few, and the material performance index finally reaching is as follows:

Initial permeability μ _i: 13000 ± 20%

Saturation induction density B _s:>=430mT (25 DEG C)

Curie temperature T _c:>=120 DEG C

Coercive force H _c:≤10A/m

Quality factor Q:10kHz, Q >=80; 50kHz, Q >=25; 100kHz, Q >=15

Permeability frequency characteristics: 10kHz, μ _i>=12500; 100kHz, μ _i>=12500; 200kHz, μ _i>=12000;

Temperature factor α _μ:≤| ± 0.5| × 10 ^-6(20～80 DEG C)

Impedance characteristic Z:1.8～2.5k Ω (10kHz～500kHz).

Embodiment

10kHz initial permeability μ provided by the invention _i=13000 ± 20%, temperature factor α in the time of 20～80 DEG C _μ≤ | ± 0.5| × 10 ^-6, 10kHz quality factor Q>=80,100kHz～500kHz impedance Z=1.8～2.5k Ω, and 200kHz magnetic permeability μ _ibeing described as follows of>=12000 MnZn Ferrite Material and preparation process:

1. formula:

Choose 52.0～54.0mol%Fe ₂o ₃, 19.0～24.0mol%ZnO, 0.01～0.05mol%NiO, all the other are MnO (Mn ₃o ₄as starting material)

2. a ball milling

To in ball mill, mix with material loading powder 1～3 hour time;

3. pre-burning

Step 2 gained ball milling material is dried, and pre-burning 1～4 hour in 850～950 DEG C of stoves;

4. doping

Step 3 gained material powder is added by weight to two or more combinations of following doping agent: 0.01～0.08wt%CaCO ₃, 0.01～0.10wt%MoO ₃, 0.01～0.08wt% nano-TiO ₂, 0.01～0.04wt%Bi ₂o ₃, 0.005～0.02wt%SiO ₂, 0.01～0.12wt%V ₂o ₅, 0.005～0.04wt%Nb ₂o ₅with 0.005～0.04wt%B ₂o ₃.Described nano-TiO ₂refer to that particle diameter is less than or equal to the TiO of 100nm ₂particulate.

5. secondary ball milling

The Preburning material that adds impurity is put into ball mill, add the deionized water that pan feeding weighs 1.6 times, ball milling 1～4 hour, makes the mean particle size of Preburning material at 1.0 ± 0.1 μ m;

6. moulding

Step 5 gained material powder is added to 8～12wt% organic binder bond by weight, mix, after granulation, on press, granular powder is pressed into blank;

7. sintering

Step 6 gained blank is placed in to sintering in atmosphere sintering furnace, at 1000～1370 DEG C of temperature sections, volume ratio O ₂/ N ₂=1/999, at 1370～1420 DEG C of temperature sections, O ₂/ N ₂=4/96, be incubated 5～8 hours; Carry out balanced atmosphere sintering at temperature descending section.

8. test:

Step 7 gained sample is carried out to electromagnetic performance test.

By the inductance L of same favour TH2828 LCR test set test sample, suitably adjust coiling both end voltage value U _sit is met: U _s=4.44NfA _eb, the initial permeability of sample is calculated according to following formula:

${\mathrm{\&mu;}}_i=\frac{L\&times;{10}^7}{2N^{2}h\ln D/d}---\left(1\right)$

The inductance that wherein L is sample, N is number of turns, and h is thickness of sample, and D is sample external diameter, and d is sample internal diameter, f is test frequency, A _efor the net sectional area of sample.Test condition is: f=10kHz, B≤0.25mT.Draw μ in conjunction with temperature control box _i-T graphic representation, uses epitaxial method to determine Curie temperature T _c.

The test condition of sample frequency response characteristic is: f=10kHz～1MHz, B≤0.25mT.

Sample impedance is calculated according to following formula:

$Z=\mathrm{\&omega;}\frac{{\mathrm{\&mu;}}_0{N}^{2}h}{2\mathrm{\&pi;}}\ln \frac{r_2}{r_1}{\mathrm{\&mu;}}^{\&prime;\&prime;}+\mathrm{j\&omega;}\frac{{\mathrm{\&mu;}}_0{N}^{2}h}{2\mathrm{\&pi;}}\ln \frac{r_2}{r_1}{\mathrm{\&mu;}}^{\&prime;}---\left(2\right)$

Test condition is: f=10kHz～500kHz, B≤0.25mT.

Sample temperature coefficient calculates according to following formula:

${\mathrm{\&alpha;}}_{\mathrm{\&mu;}}=\frac{1}{\mathrm{\&mu;}}\&CenterDot;\frac{\&PartialD;\mathrm{\&mu;}}{\&PartialD;T}=\frac{{\mathrm{\&mu;}}_1-{\mathrm{\&mu;}}_{\mathrm{ref}}}{{\mathrm{\&mu;}}_{\mathrm{ref}}(T_1-T_{\mathrm{ref}})}---\left(3\right)$

Test condition is: f=10kHz, B≤0.25mT, T=20～80 DEG C.

With the magnetic hysteresis loop of IWATSU SY-8232B-H analyser test sample, test condition is: f=0.1kHz, H=1600A/m.

Be below the specific embodiment of the present invention, technical characterictic of the present invention is described further, but the present invention is not limited in these embodiment.

Embodiment 1～4:

1. formula

Embodiment 1～4 major ingredient formula sees the following form:

2. a ball milling

To in ball mill, mix with material loading powder 1 hour time;

3. pre-burning

Step 2 gained ball milling material is dried, under 60MPa, be pressed into cake, and pre-burning 2 hours in 900 DEG C of stoves;

4. doping

Step 3 gained material powder is added to doping agent shown in following table by weight:

5. secondary ball milling

The Preburning material that adds impurity is put into ball mill, add the deionized water that pan feeding weighs 1.6 times, ball milling 2 hours, makes the mean particle size of Preburning material at 1.0 ± 0.1 μ m;

6. moulding

Step 5 gained material powder is added to 12wt% organic binder bond by weight, mix, after granulation, on press, granular powder is pressed into blank;

7, sintering

Step 6 gained blank is placed in to sintering in atmosphere sintering furnace, at 1000～1400 DEG C of temperature sections, volume ratio O ₂/ N ₂=1/999, at 1400 DEG C of insulations 6 hours, O ₂/ N ₂=4/96; Carry out balanced atmosphere sintering at temperature descending section.

The MnZn Ferrite Material of preparing through above technique, its performance index are as follows:

Embodiment 1～4 test result is as follows:

Claims (7)

1. low-temperature coefficient high resistance High Initial Permeability MnZn Ferrite Materials, is characterized in that, comprises following component:

Principal constituent: Fe ₂o ₃: 52.0～54.0mol%, ZnO:19.0～24.0mol%, NiO:0.01～0.05mol%, surplus is MnO;

Also comprise at least two kinds in following additives: 0.01～0.08wt%CaCO ₃, 0.01～0.10wt%MoO ₃, 0.01～0.08wt% nano-TiO ₂, 0.01～0.04wt%Bi ₂o ₃, 0.005～0.02wt%SiO ₂, 0.01～0.12wt%V ₂o ₅, 0.005～0.04wt%Nb ₂o ₅with 0.005～0.04wt%B ₂o ₃.

2. low-temperature coefficient high resistance High Initial Permeability MnZn Ferrite Materials as claimed in claim 1, is characterized in that, component is:

Principal constituent: Fe ₂o ₃: 52.5mol%, ZnO:21.80mol%, NiO:0.01mol%, MnO:25.69mol%;

Additive: 0.03wt%CaCO ₃, 0.08wt%MoO ₃, 0.02wt% nano-TiO ₂, 0.02wt%Bi ₂o ₃, 0.005wt%SiO ₂.

3. low-temperature coefficient high resistance High Initial Permeability MnZn Ferrite Materials as claimed in claim 1, is characterized in that, component is:

Principal constituent: Fe ₂o ₃: 52.5mol%, ZnO:22mol%, NiO:0.02mol%, MnO:25.48mol%;

Additive: 0.03wt%CaCO ₃, 0.08wt%MoO ₃, 0.03wt% nano-TiO ₂, 0.02wt%Bi ₂o ₃, 0.005wt%SiO ₂.

4. low-temperature coefficient high resistance High Initial Permeability MnZn Ferrite Materials as claimed in claim 1, is characterized in that, component is:

Principal constituent: Fe ₂o ₃: 52.7mol%, ZnO:22.3mol%, NiO:0.03mol%, MnO:24.97mol%;

Additive: 0.03wt%CaCO ₃, 0.08wt%MoO ₃, 0.02wt% nano-TiO ₂, 0.03wt%Bi ₂o ₃, 0.005wt%SiO ₂.

5. low-temperature coefficient high resistance High Initial Permeability MnZn Ferrite Materials as claimed in claim 1, is characterized in that, component is:

Principal constituent: Fe ₂o ₃: 52.7mol%, ZnO:22.5mol%, NiO:0.04mol%, MnO:24.76mol%;

Additive: 0.03wt%CaCO ₃, 0.08wt%MoO ₃, 0.03wt% nano-TiO ₂, 0.03wt%Bi ₂o ₃, 0.005wt%SiO ₂.

6. the preparation method of low-temperature coefficient high resistance High Initial Permeability MnZn Ferrite Materials as claimed in claim 1, is characterized in that, comprises the steps:

1. formula:

Choose 52.0～54.0mol%Fe ₂o ₃, 19.0～24.0mol%ZnO, 0.01～0.05mol%NiO, all the other are MnO, wherein with Mn ₃o ₄as the starting material of MnO;

2. a ball milling

To in ball mill, mix with material loading powder 1～3 hour time;

3. pre-burning

Step 2 gained ball milling material is dried, and pre-burning 1～4 hour in 850～950 DEG C of stoves;

4. doping

Step 3 gained material powder is added to two or more of following doping agent: 0.01～0.08wt%CaCO by weight ₃, 0.01～0.10wt%MoO ₃, 0.01～0.08wt% nano-TiO ₂, 0.01～0.04wt%Bi ₂o ₃, 0.005～0.02wt%SiO ₂, 0.01～0.12wt%V ₂o ₅, 0.005～0.04wt%Nb ₂o ₅with 0.005～0.04wt%B ₂o ₃;

5. secondary ball milling

The Preburning material that adds impurity is put into ball mill, add the deionized water that pan feeding weighs 1.6 times, ball milling 1～4 hour, makes the mean particle size of Preburning material at 1.0 ± 0.1 μ m;

6. moulding

Step 5 gained material powder is added to 8～12wt% organic binder bond by weight, mix, after granulation, on press, granular powder is pressed into blank;

7. sintering

Step 6 gained blank is placed in to sintering in atmosphere sintering furnace, at 1000～1370 DEG C of temperature sections, volume ratio O ₂/ N ₂=1/999, at 1370～1420 DEG C of temperature sections, O ₂/ N ₂=4/96, be incubated 5～8 hours; Carry out balanced atmosphere sintering at temperature descending section.

7. the preparation method of low-temperature coefficient high resistance High Initial Permeability MnZn Ferrite Materials as claimed in claim 6, is characterized in that, in described step 1, each component is:

Fe ₂o ₃: 52.7mol%, ZnO:22.5mol%, NiO:0.04mol%, MnO:24.76mol%; In described step 4, additive is:

0.03wt%CaCO ₃, 0.08wt%MoO ₃, 0.03wt% nano-TiO ₂, 0.02wt%Bi ₂o ₃, 0.005wt%SiO ₂.