CN115925405A - NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature and preparation method thereof - Google Patents
NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a NiCuZn soft magnetic ferrite material with high magnetic conductivity and high Curie temperature and a preparation method thereof, the material comprises the following components by mass percent: fe 2 O 3 66.22wt% -68.65 wt%; 18.30 to 22.15 weight percent of ZnO; 7.75 to 9.85 weight percent of NiO; the balance being CuO; the doping component contains Y 2 O 3 、MoO 3 、V 2 O 5 And MnCO 3 Wherein Y is 2 O 3 、MoO 3 、V 2 O 5 、MnCO 3 The contents of the components are respectively 0.05wt% -0.10 wt%, 0.06wt% -0.18 wt%, 0.05wt% -0.15 wt% and 0.04wt% -0.12 wt% of the mass of the main component. The invention relates to a NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperatureThe magnetic conductivity is as high as 2011, the Curie temperature is as high as 145 ℃, and the specific loss coefficient is 28.78 multiplied by 10 under 0.1MHz ‑6 Saturation magnetic flux density B s =352mT (4000A/m, 10 kHz). Has magnetic performance far superior to that of the same material, and has simple process and reliable performance.
Description
Technical Field
The invention relates to the technical field of soft magnetic ferrite electronic information materials, in particular to a NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature and a preparation method thereof.
Background
The NiCuZn soft magnetic ferrite material is used as a very important electronic information material, has very wide application in the fields of communication, electronics, aerospace, military science and technology and the like, and has high resistivity rho, high cut-off frequency and high initial permeability mu i The low-loss and low-temperature coefficient can be widely applied to high-frequency inductance magnetic cores, near Field Communication (NFC) systems, laminated chip inductors (MLCI), anti-EMI devices and the like. The initial permeability of the existing NiCuZn soft magnetic ferrite material is mostly lower than 1600, and the Curie temperature (T) of the NiCuZn soft magnetic ferrite material is generally higher than the permeability of the NiCuZn soft magnetic ferrite material c ) The lower, such as: niZn series material T with initial magnetic conductivity more than 1500 and room temperature saturation magnetic flux density more than 250mT c About 100 ℃ with a higher T c The permeability of the NiZn series materials is generally less than 1000. Low T c Meaning that the narrower the operating temperature range of the material, limits its application in many areas.
CN 101236819A discloses a nickel-copper-zinc ferrite and a manufacturing method thereof, the ferrite comprises a main component and an auxiliary component, wherein the main component is calculated by mole percent: fe 2 O 3 :48mol% -50 mol%, niO:13mol% to 16mol%, znO:29mol% to 31.5mol%, cuO:4.5mol% -6.5 mol%; the accessory components comprise vanadium oxide, molybdenum oxide and titanium oxide, and the total adding content of the accessory components is 0.01wt% -0.08 wt%. The prepared nickel-copper-zinc ferrite material has initial permeability (mu) i )1200±20％，T c Not lower than 160 deg.C, and saturated magnetic flux density not lower than 360mT.
CN 104030669A discloses a preparation method of NiZn ferrite by filter pressing. The main components are as follows by mole percentage: fe 2 O 3 ：48～54mol％、ZnO：30～32mol％、NiO：3.5～10mol％、CuO：8～15mol percent; the doping agent is calculated according to the weight percentage: v 2 O 5 :0 to 3 weight percent. The optimum magnetic properties obtained were as follows: mu.s i 2100, inverse of specific loss factor 5X 10 4 ，T c The saturation magnetic flux density was 240mT at 98 ℃.
CN 109320227A discloses a NiCuZn ferrite material, a preparation method and application thereof. The NiCuZn ferrite material is mainly made of Fe 2 O 3 ZnO, niO and CuO, fe based on 100% of the total molar amount of NiCuZn ferrite material 2 O 3 The mol percent of the NiO is 48.8 to 50mol percent, the mol percent of the ZnO is 32 to 34mol percent, the mol percent of the NiO is 6.5 to 8mol percent, and the mol percent of the CuO is 8.5 to 12.7mol percent. The prepared NiCuZn ferrite material has a real part mu 'of complex permeability of 1600-2000 and an imaginary part mu' of not more than 50 within the range of 100-300 kHz, saturation magnetic induction intensity Bs of not less than 240mT and coercive force H at 100kHz, 1194A/m and 25 DEG C c Less than or equal to 60A/m, curie temperature T c Is 95-110 ℃.
In the above-mentioned patent publications, some of the initial permeance is low, some of the curie temperature is low, and some of the saturation magnetic flux density is low, and it is difficult to achieve a high initial permeability, a high curie temperature, and a high saturation magnetic flux density at the same time. These problems have made it impossible to meet the use requirements for soft magnetic materials such as miniature high-quality inductors, pulse transformers, electromagnetic interference suppressors, and the like. With the development trend of miniaturization, high power and wide temperature of electronic products, higher requirements are put forward on electronic components, so that the NiCuZn soft magnetic ferrite material is required to have high initial permeability and high Curie temperature, and the characteristics of high current resistance, low loss and the like are ensured. The current NiCuZn soft magnetic ferrite material and the manufacturing process can not meet the requirements.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a high-permeability high-Curie temperature NiCuZn soft magnetic ferrite material comprises main components and doping components, wherein the main components comprise, by mass: fe 2 O 3 66.22wt% -68.65 wt%; 18.30 to 22.15 weight percent of ZnO; 7.75 to 9.85 weight percent of NiO; the balance being CuO;
the doping component contains Y 2 O 3 、MoO 3 、V 2 O 5 And MnCO 3 Wherein, Y 2 O 3 The content of the main component is 0.05 to 0.10 weight percent of the mass of the main component, and MoO 3 The content of V is 0.06wt% -0.18 wt% of the mass of the main component 2 O 5 The content of MnCO accounts for 0.05 to 0.15 weight percent of the mass of the main component 3 The content is 0.04wt% -0.12 wt% of the mass of the main component.
Preferably, the total mass of the doping components is not more than 0.55wt% of the mass of the main component.
Preferably, the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature has initial magnetic permeability of 1665-2320 and specific loss coefficient of 13 multiplied by 10 under 100kHz test frequency -6 -35.5×10 -6 The Curie temperature is 124-145 ℃, the saturation magnetic flux density is 329-352mT, and the coercive force is 18-28.5A/m.
Preferably, the density of the high-permeability high-Curie temperature NiCuZn soft magnetic ferrite material is 5.17-5.37g/cm 3 。
The preparation method of the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature comprises the following steps:
mixing Fe 2 O 3 Uniformly mixing the powder, znO powder, niO powder and CuO powder to obtain a mixture A;
granulating and pre-sintering the mixture A to obtain a pre-sintered material;
crushing the pre-sintered material, adding doping components, performing ball milling and uniformly mixing to obtain a mixture B;
granulating and pressing the mixture B to obtain a sample ring blank;
and sintering the sample ring blank to obtain the high-permeability high-Curie-temperature NiCuZn soft magnetic ferrite material.
Preferably, fe is added 2 O 3 And (3) uniformly mixing the powder, znO powder, niO powder and CuO powder to obtain a mixture A:
mixing Fe 2 O 3 Powder, znO powder, niO powder and CuO powder wet process mixing, when wet process mixing, the steel ball: ultrapure water: the weight ratio of the powder is 5: (1.3-1.7): 1, ball milling rotation speed is 100-120 r/min, and wet ball milling mixing time is 3-6h; and after wet mixing, adding a PVA solution into the slurry, and performing wet mixing and grinding again, wherein the adding amount of the PVA solution is 4-6 wt%, and the ball milling time is 20-40min after adding the PVA solution.
Preferably, when the mixture A is granulated, the granulation method is red spray granulation, the outlet temperature of a spray tower is 85-95 ℃, the inlet temperature is 160-180 ℃ and the granulation particle size is 120-180 mu m in the granulation process, the pre-sintering temperature is 930-970 ℃ during pre-sintering, and the heat preservation time is 2-3h.
Preferably, the pre-sintering material is crushed to 280-380 mu m, when the pre-sintering material crushed material and the doping component are uniformly milled and mixed, the mass ratio of milling balls to ultrapure water to the material is 4 (1.3-1.7) to 1, the milling speed is 380-420 r/min, and the milling time is 5.5-6.5h;
and ball-milling and uniformly mixing the pre-sintered material crushed material and the doping component, adding a PVA solution, carrying out ball-milling again by a wet method, wherein the adding amount of the PVA solution is 4-6 wt%, and the ball-milling time is 20-40min after the PVA solution is added.
Preferably, when the mixture B is granulated, the granulation method is black spray granulation, the outlet temperature of a spray tower is 80-90 ℃, the inlet temperature is 170-190 ℃ and the granulation particle size is 70-130 mu m in the granulation process;
when in compression molding, zinc stearate accounting for 0.10 to 0.14 weight percent of the weight of the granulated powder is added into the granulated powder as a release agent, the molding mode adopts bidirectional pressurization and cold press molding, and the molding pressure is 9.8 to 10.2MPa.
Preferably, when sintering is performed on the sample ring blank, a gradient heating process is adopted for sintering, and when sintering is performed by adopting the gradient heating process:
heating to 440-500 ℃ at the speed of 1.3-1.7 ℃/min, preserving heat for 1.8-2.2h, then heating to 900 ℃ at the speed of 2.8-3.2 ℃/min, heating to 1130-1170 ℃ at the speed of 1.8-2.2 ℃/min, preserving heat for 2-3h, and then naturally cooling along with the furnace to obtain the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature.
The invention has the following beneficial effects:
the optimal magnetic property of the NiCuZn soft magnetic ferrite material with high magnetic conductivity and high Curie temperature is as follows: initial permeability μ at a test frequency of 100kHz i 2011, specific loss coefficient 28.78 × 10 -6 Curie temperature T c =145 ℃, saturation magnetic flux density B s =352mT (10kHz, 4000A/m), coercive force H c =28.41A/m. In addition, the NiCuZn soft magnetic ferrite material with high magnetic conductivity and high Curie temperature has the characteristics of high working frequency and small temperature coefficient. In conclusion, the high-permeability high-Curie-temperature NiCuZn soft magnetic ferrite material disclosed by the invention not only has high initial permeability and high Curie temperature, but also has higher saturation magnetic flux density and low loss. The invention can realize the requirements of miniaturized, high working temperature and low loss inductive devices on magnetic materials: high mu i 、T c And B s Lower tg δ/μ i And H c 。
Drawings
FIG. 1 is μ of a NiCuZn soft magnetic ferrite sample prepared in example 2 i And tg δ as a function of frequency;
FIG. 2 is a μ of a NiCuZn soft magnetic ferrite sample prepared in example 2 i The temperature dependence;
fig. 3 is a B-H curve of a NiCuZn soft magnetic ferrite sample prepared in example 2.
Detailed Description
The invention is further described below with reference to the figures and examples.
The overall idea of the invention is as follows: the main component adopted by the invention comprises Fe 2 O 3 NiO, znO and CuOThese several main components determine the main technical parameters (such as initial permeability, curie temperature, saturation flux density) of the NiCuZn ferrite material. In addition, the invention uses Y for the first time 2 O 3 、MoO 3 、V 2 O 5 And MnCO 3 The trace element co-doping technology can play the beneficial effect of each trace element and the synergistic effect of ions to the maximum extent. Proper amount of V 2 O 5 The doping can make ferrite form liquid phase sintering and increase magnetic conductivity, and the liquid phase formed in the sintering process is helpful for Y 2 O 3 、MoO 3 、MnCO 3 Trace elements enter the crystal boundary to play a role, and a small amount of MoO 3 The doping of (2) can increase the ferrite grain size, improve the uniformity and increase the initial permeability, but also can slightly reduce the Curie temperature. And Y is 2 O 3 Can influence the super exchange function between the A-site ions and the B-site ions of the tetrahedron of the ferrite, thereby improving the Curie temperature of the ferrite. In addition, a trace amount of MnCO 3 The addition of (2) can increase the lattice constant and improve the initial permeability and the Q value. Therefore, the performance of the NiCuZn ferrite material is further optimized through the synergistic effect of a plurality of trace dopants, the high-permeability high-Curie temperature NiCuZn soft magnetic ferrite material with excellent comprehensive performance is finally obtained, and the requirements of miniaturized, wide-temperature and high-power inductive devices on soft magnetic materials are met.
The raw materials used in the invention are industrial raw materials, and the invention has the advantages of low price, large yield, no toxicity, no harm, simple preparation process, energy saving, high efficiency and convenient industrial popularization.
Specifically, the raw materials of the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature comprise main components and doping components, and the main components mainly comprise the following components in percentage by mass: fe 2 O 3 66.22 to 68.65 weight percent; 18.30 to 22.15 weight percent of ZnO; 7.75 to 9.85 weight percent of NiO; the balance being CuO.
The doping component contains Y 2 O 3 、MoO 3 、V 2 O 5 And MnCO 3 Wherein Y is 2 O 3 The content is 0.05wt% -0.10 wt% of the main component，MoO 3 The content of the main component is 0.06wt% -0.18 wt%, V 2 O 5 The content of MnCO accounts for 0.05 to 0.15 weight percent of the mass of the main component 3 The content is 0.04wt% -0.12 wt% of the mass of the main component. The content of the doping component is not more than 0.55wt% of the mass of the main component.
The preparation method of the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature comprises the following steps:
(1) Mixing raw materials: taking Fe with purity respectively 2 O 3 Powder with the weight percentage of more than or equal to 99.40 percent, niO with the weight percentage of more than or equal to 99.20 percent, znO with the weight percentage of more than or equal to 99.70 percent and CuO with the weight percentage of more than or equal to 99.00 percent is filled into a roller ball mill, and wear-resistant steel balls and ultrapure water are filled into the roller ball mill, the steel balls in a ball milling tank are as follows: ultrapure water: the weight ratio of the powder is 5: (1.5 ± 0.2): 1, rotating speed of 100-120 r/min, ball milling for 3-6h, adding 4-6 wt% of PVA glue after finishing, and continuously wet milling for 20-40min to obtain a mixture A.
(2) And (3) red spray granulation: carrying out red spray granulation on the mixture A, wherein the outlet temperature of a spray tower is 85-95 ℃, the inlet temperature is 170 +/-10 ℃, and the particle size of the obtained material is 150 +/-30 mu m;
(3) High-temperature pre-sintering: pre-burning the red spray granulated material obtained in the step (2), wherein the pre-burning temperature is 930-970 ℃, preserving heat for 2.5 +/-0.5 h, and naturally cooling after heat preservation;
(4) Doping trace elements: crushing the pre-sintered material obtained in the step (3) to obtain a crushed material with a particle size range of 330 +/-50 mu m, and adding a doping component Y 2 O 3 :0.05wt％～0.10wt％；MoO 3 :0.06wt％～0.18wt％；V 2 O 5 :0.05wt％～0.15wt％；MnCO 3 :0.04wt％～0.12wt％。
(5) Planetary ball milling: putting the mixture obtained in the step (4) into a planetary ball mill for ball milling, mixing the mixture according to the mass ratio of the grinding balls to ultrapure water to the mixture =4 to (1.5 +/-0.2) to 1, ball milling for 5.5-6.5h at the rotating speed of 400 +/-20 r/min, and then adding 4-6 wt% of PVA glue for continuously ball milling for 20-40min to obtain a mixture B;
(6) And (3) black spray granulation: carrying out black spray granulation on the mixture B prepared in the step (5), wherein the outlet temperature of a spray tower is 80-90 ℃, the inlet temperature is 180 +/-10 ℃, and the particle size of the obtained material is 100 +/-30 mu m;
(7) Cold press molding: adding zinc stearate as a release agent into the powder prepared in the step (6) according to the weight percent (0.12 +/-0.02) of the material weight, performing cold press molding in a two-way pressurizing mode at the molding pressure of 10 +/-0.2 MPa,
(8) High-temperature gradient sintering: and (3) placing the sample ring blank in the step (7) in a sintering furnace at 1150 +/-20 ℃ for sintering and preserving heat for 2.5 +/-0.5 h, wherein the temperature rise gradient is as follows: heating at the rate of 1.5 +/-0.2 ℃/min when the temperature is between the room temperature and 470 +/-30 ℃, preserving heat at the temperature of 470 +/-30 ℃ for 2 +/-0.2h, heating at the rate of 3 +/-0.2 ℃/min when the temperature is between 470 +/-30 ℃ and 900 ℃, then heating to 1150 +/-20 ℃ at the rate of 2 +/-0.2 ℃/min, preserving heat for 2.5 +/-0.5 h, naturally cooling to room temperature after finishing, and discharging to obtain the high-permeability high-Curie temperature NiCuZn soft magnetic ferrite material. The density of the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature is 5.27 +/-0.1 g/cm 3 。
Example 1:
the preparation method of the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature comprises the following steps:
(1) Mixing raw materials: taking Fe with purity respectively 2 O 3 The raw material powder comprises more than or equal to 99.40 percent of NiO, more than or equal to 99.20 percent of ZnO, more than or equal to 99.70 percent of CuO and more than or equal to 99.00 percent of CuO, and is weighed according to the following mixture ratio: fe 2 O 3 66.22wt%; 22.15 percent of ZnO; 7.75wt% of NiO; the balance being CuO. Loading into a roller ball mill, and loading wear-resistant steel balls and ultrapure water, wherein the steel balls in a ball milling tank: ultrapure water: the weight ratio of the powder is 5:1.7:1, rotating speed of 100 r/min, ball milling for 3h, adding 6wt% of PVA glue after ball milling, and continuously wet milling for 40min to obtain a mixture A.
(2) And (3) red spray granulation: carrying out red spray granulation on the mixture A, wherein the outlet temperature of a spray tower is 90 ℃, the inlet temperature is 180 ℃, and the particle size range of the obtained material is 150 +/-30 mu m;
(3) High-temperature pre-sintering: pre-burning the red spray granulated material obtained in the step (2), setting the pre-burning temperature to be 930 ℃, preserving heat for 2 hours, and naturally cooling after heat preservation;
(4) Doping trace elements: crushing the pre-sintered material obtained in the step (3) to obtain a crushed material with a particle size range of 330 +/-50 mu m, and adding a doping component Y 2 O 3 :0.10wt％；MoO 3 :0.06wt％；V 2 O 5 :0.15wt％；MnCO 3 0.06wt%, and the addition amount of each component of the doping component is calculated by the content of the main component.
(5) Planetary ball milling: putting the doped and crushed pre-sintering powder obtained in the step (4) into a planetary ball mill for ball milling, mixing the pre-sintering powder according to the mass ratio of grinding balls to ultrapure water to materials = 4: 1.3:1, carrying out ball milling for 6h at the rotating speed of 380 r/min, and adding 6wt% PVA glue for ball milling for 20min after the ball milling is finished to obtain a mixture B;
(6) And (3) black spray granulation: carrying out black spray granulation on the mixture B prepared in the step (5), wherein the outlet temperature of a spray tower is 80 ℃, the inlet temperature is 170 ℃, and the particle size of the obtained material is 100 +/-30 microns;
(7) And (3) cold press molding: adding zinc stearate into the powder prepared in the step (6) according to 0.10wt% of the material weight as a release agent, performing cold press molding in a two-way pressurizing mode at the molding pressure of 9.8MPa,
(8) High-temperature gradient sintering: and (3) sintering the sample ring blank in the step (7) at 1170 ℃ in a sintering furnace and preserving heat for 3h, wherein the temperature rise gradient is as follows: heating at the rate of 1.7 ℃/min when the temperature is between the room temperature and 440 ℃, preserving heat for 2.2h at the rate of 3.2 ℃/min when the temperature is between 440 ℃ and 900 ℃, then heating to 1170 ℃ at the rate of 2.2 ℃/min, preserving heat for 3h, naturally cooling to room temperature after the temperature is up, and discharging to obtain the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature. The high magnetic conductanceThe density of the NiCuZn soft magnetic ferrite material with high Curie temperature is 5.17g/cm 3 。
Example 2:
the preparation method of the high-permeability high-curie-temperature NiCuZn soft magnetic ferrite material comprises the following steps of:
(1) Mixing raw materials: taking Fe with purity respectively 2 O 3 More than or equal to 99.40 percent of powder, more than or equal to 99.20 percent of NiO, more than or equal to 99.70 percent of ZnO and more than or equal to 99.00 percent of CuO, and the weight percentages are as follows: fe 2 O 3 67.47wt%; 21.03 percent of ZnO; 9.24wt% of NiO; the balance being CuO. Loading into a roller ball mill, and loading wear-resistant steel balls and ultrapure water, wherein the steel balls in a ball milling tank: ultrapure water: the weight ratio of the powder is 5:1.5:1, ball milling for 5 hours at the rotating speed of 115 r/min by a ball mill, and adding 5wt% of PVA (polyvinyl alcohol) glue to wet-grind for 30 minutes to obtain a mixture A.
(2) And (3) red spray granulation: carrying out red spray granulation on the mixture A, wherein the outlet temperature of a spray tower is 95 ℃, the inlet temperature is 190 ℃, and the particle size range of the obtained material is 150 +/-30 mu m;
(3) High-temperature pre-sintering: pre-burning the red spray granulated material obtained in the step (2), keeping the temperature of the pre-burning at 950 ℃ for 3 hours, and naturally cooling along with the furnace after the heat preservation is finished;
(4) Doping trace elements: crushing the pre-sintered material obtained in the step (3), wherein the particle size range of the obtained crushed material is 330 +/-50 microns, and then adding the following doping components: y is 2 O 3 :0.08wt％；MoO 3 :0.12wt％；V 2 O 5 :0.1wt％；MnCO 3 0.04wt%, and the addition amount of each component of the doping component is calculated as the content of the main component.
(5) Planetary ball milling: putting the mixture obtained in the step (4) into a planetary ball mill for ball milling, mixing the mixture according to the mass ratio of the grinding balls to the ultrapure water to the material = 4: 1.5:1, carrying out ball milling for 5.5h at the rotating speed of 420 r/min, and then adding 5wt% PVA (polyvinyl alcohol) glue for ball milling for 30min to obtain a mixture B;
(6) And (3) black spray granulation: carrying out black spray granulation on the mixture B prepared in the step (5), wherein the outlet temperature of a spray tower is 85 ℃, the inlet temperature is 180 ℃, and the particle size of the obtained material is 100 +/-30 microns;
(7) Cold press molding: adding zinc stearate into the powder prepared in the step (6) according to 0.14wt% of the weight of the powder to serve as a release agent, performing cold press molding in a bidirectional pressurizing mode, wherein the molding pressure is 10.2MPa,
(8) High-temperature gradient sintering: and (3) placing the sample ring blank in the step (7) in a sintering furnace at 1150 ℃ for sintering and preserving heat for 2.5h, wherein the temperature rise gradient is as follows: heating at the rate of 1.5 ℃/min when the room temperature is between 470 ℃, preserving heat for 2h at the temperature of 470 ℃ and at the rate of 3 ℃/min when the temperature of 470 ℃ is between 900 ℃, then heating to 1150 ℃ at the rate of 2 ℃/min and preserving heat for 2.5h, naturally cooling to the room temperature after the heating is finished, and discharging to obtain the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature. The density of the high-permeability high-Curie temperature NiCuZn soft magnetic ferrite material is 5.37g/cm 3 。
Example 3:
the preparation method of the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature comprises the following steps:
(1) Mixing raw materials: taking Fe with purity respectively 2 O 3 More than or equal to 99.40 percent of powder, more than or equal to 99.20 percent of NiO, more than or equal to 99.70 percent of ZnO and more than or equal to 99.00 percent of CuO, which are weighed according to the following mixture ratio: fe 2 O 3 68.65wt%; 18.30 percent of ZnO; 9.85wt% of NiO; the balance being CuO. Loading into a roller ball mill, and loading wear-resistant steel balls and ultrapure water, wherein the steel balls in a ball milling tank: ultrapure water: the weight ratio of the powder is 5:1.3:1, rotating at 120 r/min, ball-milling for 6h, adding 4wt% of PVA glue, and wet-milling for 20min to obtain a mixture A.
(2) And (3) red spray granulation: carrying out red spray granulation on the mixture A, wherein the outlet temperature of a spray tower is 85 ℃, the inlet temperature is 170 ℃, and the particle size of the obtained material is 150 +/-30 mu m;
(3) High-temperature pre-sintering: pre-burning the red spray granulated material obtained in the step (2), keeping the pre-burning temperature at 970 ℃, keeping the temperature for 2.5 hours, and naturally cooling after the heat preservation is finished;
(4) Doping trace elements: crushing the pre-sintered material obtained in the step (3) to obtain a crushed material with the particle size of 330 +/-50 microns, and adding a doping component Y 2 O 3 :0.05wt％；MoO 3 :0.18wt％；V 2 O 5 :0.05wt％；MnCO 3 0.12wt%, and the addition amount of each component of the doping component is calculated by the content of the main component.
(5) Planetary ball milling: putting the ingredients obtained in the step (4) into a planetary ball mill for ball milling, mixing the ingredients according to the mass ratio of the grinding balls to the ultrapure water to the ingredients = 4: 1.7:1, carrying out ball milling for 6.5h at the rotating speed of 400 r/min, and then adding 4wt% of PVA glue for ball milling for 40min to obtain a mixture B;
(6) And (3) black spray granulation: carrying out black spray granulation on the mixture B prepared in the step (5), wherein the outlet temperature of a spray tower is 90 ℃, the inlet temperature is 190 ℃, and the particle size of the obtained material is 100 +/-30 microns;
(7) Cold press molding: adding zinc stearate into the powder prepared in the step (6) according to 0.12wt% of the material weight as a release agent, performing cold press molding in a two-way pressurizing mode at the molding pressure of 10MPa,
(8) High-temperature gradient sintering: and (3) placing the sample ring blank in the step (7) in a sintering furnace at 1130 ℃ for sintering and preserving heat for 2h, wherein the temperature rise gradient is as follows: heating at the rate of 1.3 ℃/min when the temperature is between the room temperature and 500 ℃, preserving heat for 1.8h at the rate of 2.8 ℃/min when the temperature is between 500 ℃ and 900 ℃, then heating to 1130 ℃ at the rate of 1.8 ℃/min, preserving heat for 2h, naturally cooling to the room temperature after the temperature is up, and discharging to obtain the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature. The density of the high-permeability high-Curie temperature NiCuZn soft magnetic ferrite material is 5.25g/cm 3 。
Referring to fig. 1-3, the results of the performance tests of the samples prepared in each example are shown in table 1:
TABLE 1
As can be seen from Table 1, the samples obtained in example 2 have relatively excellent comprehensive properties, namely initial permeability mu at 100kHz testing frequency i 1665-2320, and specific loss coefficient of 28.78 × 10 -6 Curie temperature T c =145 ℃, saturation magnetic flux density B s =352mT (10kHz, 4000A/m), coercive force H c =28.41A/m. In addition, the device also has the characteristics of high working frequency, small temperature coefficient and the like. Furthermore, it is observed from the above examples that the sample of example 1 has a relatively highest μ i (2320) And the minimum specific loss factor (13.24 × 10) -6 )。
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Any changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (10)
1. A high-permeability high-Curie temperature NiCuZn soft magnetic ferrite material is characterized by comprising a main component and a doping component, wherein the main component comprises the following components in percentage by mass: fe 2 O 3 66.22wt% -68.65 wt%; 18.30 to 22.15 weight percent of ZnO; 7.75 to 9.85 weight percent of NiO; the balance is CuO;
the doping component contains Y 2 O 3 、MoO 3 、V 2 O 5 And MnCO 3 Wherein, Y 2 O 3 The content of the main component is 0.05 to 0.10 weight percent of the mass of the main component, and MoO 3 The content of V is 0.06wt% -0.18 wt% of the mass of the main component 2 O 5 The content of the MnCO is 0.05wt% -0.15 wt% of the mass of the main component 3 The content is 0.04wt% -0.12 wt% of the mass of the main component.
2. A high permeability high curie temperature NiCuZn soft magnetic ferrite material as claimed in claim 1, wherein the total mass of the doping components is not more than 0.55wt% of the mass of the main component.
3. The NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature as claimed in claim 1, wherein the initial magnetic permeability of the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature is 1665-2320, and the specific loss coefficient is 13 x 10 at 100kHz test frequency -6 -35.5×10 -6 The Curie temperature is 124-145 ℃, the saturation magnetic flux density is 329-352mT, and the coercive force is 18-28.5A/m.
4. The high permeability high curie temperature NiCuZn soft magnetic ferrite material as claimed in claim 1, wherein the density of the high permeability high curie temperature NiCuZn soft magnetic ferrite material is 5.17-5.37g/cm 3 。
5. A method for preparing a high permeability high Curie temperature NiCuZn soft magnetic ferrite material according to any one of claims 1 to 4, which is characterized by comprising the following steps:
mixing Fe 2 O 3 Uniformly mixing the powder, znO powder, niO powder and CuO powder to obtain a mixture A;
granulating and pre-sintering the mixture A to obtain a pre-sintered material;
crushing the pre-sintered material, adding doping components, performing ball milling and uniformly mixing to obtain a mixture B;
granulating and pressing the mixture B to obtain a sample ring blank;
and sintering the sample ring blank to obtain the high-permeability high-Curie-temperature NiCuZn soft magnetic ferrite material.
6. The method for preparing a high permeability high Curie temperature NiCuZn soft magnetic ferrite material according to claim 5,mixing Fe 2 O 3 And uniformly mixing the powder, znO powder, niO powder and CuO powder to obtain a mixture A:
mixing Fe 2 O 3 Powder, znO powder, niO powder and CuO powder wet process mixing, when wet process mixing, the steel ball: ultrapure water: the weight ratio of the powder is 5: (1.3-1.7): 1, ball milling rotation speed is 100-120 r/min, and wet ball milling mixing time is 3-6h; and after wet mixing, adding a PVA solution into the slurry, and performing wet mixing and grinding again, wherein the adding amount of the PVA solution is 4-6 wt%, and the ball milling time is 20-40min after adding the PVA solution.
7. The preparation method of the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature as claimed in claim 5, wherein the granulation method is red spray granulation when the mixture A is granulated, the outlet temperature of a spray tower is 85-95 ℃, the inlet temperature is 160-180 ℃, the granulation particle size is 120-180 μm, the pre-sintering temperature is 930-970 ℃ during pre-sintering, and the heat preservation time is 2-3h.
8. The preparation method of the NiCuZn soft magnetic ferrite material with high magnetic conductivity and high Curie temperature according to claim 5, characterized in that the pre-sintered material is crushed to 280-380 μm, when the pre-sintered material crushed material and the doping components are ball-milled and mixed uniformly, the mass ratio of grinding balls to ultrapure water to the material is 4 (1.3-1.7) to 1, the ball-milling speed is 380-420 r/min, and the ball-milling time is 5.5-6.5h;
and ball-milling and uniformly mixing the pre-sintered material crushed material and the doping component, adding a PVA solution, carrying out ball-milling again by a wet method, wherein the adding amount of the PVA solution is 4-6 wt%, and the ball-milling time is 20-40min after the PVA solution is added.
9. The preparation method of the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature according to claim 5, wherein the granulation method is black spray granulation when the mixture B is granulated, the outlet temperature of a spray tower is 80-90 ℃, the inlet temperature is 170-190 ℃ and the granulation grain size is 70-130 μm in the granulation process;
when in compression molding, zinc stearate accounting for 0.10 to 0.14 weight percent of the weight of the granulated powder is added into the granulated powder as a release agent, and the molding mode adopts two-way pressurizing cold-pressing molding with the molding pressure of 9.8 to 10.2MPa.
10. The method for preparing the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature according to claim 5, wherein a gradient temperature rise process is adopted for sintering when the sample ring blank is sintered, and the gradient temperature rise process is adopted for sintering when:
heating to 440-500 ℃ at the speed of 1.3-1.7 ℃/min, preserving heat for 1.8-2.2h, then heating to 900 ℃ at the speed of 2.8-3.2 ℃/min, heating to 1130-1170 ℃ at the speed of 1.8-2.2 ℃/min, preserving heat for 2-3h, and then naturally cooling along with the furnace to obtain the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature.
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