CN101811861A - Nano-crystalline MnZn ferrite material with high saturation induction density and high resistivity and preparation method thereof - Google Patents

Abstract

The invention discloses a nano-crystalline MnZn ferrite material with high saturation induction density and high resistivity and a preparation method thereof; the chemical formula of the nano-crystalline MnZn ferrite material is expressed as follows: MnxZn1-xFe2-y-zNiyZrzO4, wherein x is larger than or equal to 0.2 and less than or equal to 0.9, y is larger than or equal to 0.1 and less than or equal to 0.4, and z is larger than or equal to 0.1 and less than or equal to 0.3; the preparation method for the material comprises the following steps: (1) adding Mn, Zn, Fe, Ni, Zr in the chemical formula into deionized water, heating to reach 50-70 DEG C and uniformly stirring by a magnetic stirring apparatus; (2) adding ammonia water into the mixed liquor; adjusting the pH value for co-precipitation; (3) separating precipitates and removing impurities; (4) putting the precipitates into a drying oven and dewatering in the 100 DEG C temperature; (5) shaping; (6) sintering; the addition of the Ni and Zr in the components guarantees the high saturation induction density and high resistivity of the MnZn ferrite material; and the preparation method not only has low cost, simple technique, high production efficiency, but also has low sintering temperature and less energy consumption and is beneficial to the implementation of large-scale industrialization.

Description

Nano-crystalline MnZn ferrite material of a kind of high saturated magnetic induction and high resistivity and preparation method thereof

Technical field

The present invention relates to a kind of nano-crystalline MnZn ferrite material, relate in particular to a kind of nano-crystal soft-magnetic Ferrite Material and preparation method thereof, belong to the oxidate magnetic material technical field with high saturated magnetic induction and high resistivity.

Background technology

Mn-Zn ferrite is the soft magnetic ferrite with spinel structure, because it has high-saturation magnetic induction and high resistivity simultaneously, therefore be widely used in power electronics industry, be used for making high-frequency transformer, inductor block, choke coil, write head, magnetic amplifier, electromagnetic interference instrument or the like.

Yet the development of information industry is had higher requirement to Mn-Zn ferrite, and high-quality Mn-Zn ferrite should have high saturation induction density and high resistivity to satisfy power electronic devices miniaturization, slimming, integrated development trend.Therefore, the scientific research personnel of academic research field and technical applications has launched deep research around the relation between the electromagnetic performance of Mn-Zn ferrite and its chemical ingredients, the preparation method, and hope can be developed the MnZn ferrite material of high-saturation magnetic induction and high resistivity.

Summary of the invention

The object of the present invention is to provide nano-crystalline MnZn ferrite of a kind of high saturated magnetic induction and high resistivity and preparation method thereof.

Above-mentioned technical problem of the present invention is mainly solved by following technical proposals: the nano-crystalline MnZn ferrite material of a kind of high saturated magnetic induction and high resistivity, the chemical formula of this nano-crystalline MnZn ferrite material can be expressed as: Mn _xZn _1-xFe _2-y-zNi _yZr _zO ₄, 0.2≤x≤0.9,0.1≤y≤0.4,0.1≤z≤0.3 wherein.

Because the ferritic conductive mechanism of MnZn can be based on the Fe of octahedral site ³⁺And Fe ²⁺Between electronics jump and explain Ni among the present invention ²⁺And Zr ⁴⁺After replacement Fe mixes the MnZn ferrite, Ni ²⁺Occupied the octahedral site (being the B position) of spinel structure, Zr ⁴⁺Occupied the tetrahedral site (being the A position) of spinel structure.Ni ²⁺Replace Fe and reduced the Fe ionic quantity of B position, reduced the electron amount of jump takes place, thereby improved the ferritic resistivity of MnZn.Simultaneously, Zr ⁴⁺Be a quadrivalent ion, in the process of subsequent anneal, will form stable Zr ⁴⁺-Fe ²⁺Ion pair has reduced Fe ³⁺And Fe ²⁺Between electronics jump, improved ferritic resistivity.And Ni ²⁺Occupy and make part Fe behind the B position ³⁺Transfer to the A position, thereby improved Fe ³⁺-O-Fe ³⁺Between superexchange interaction, compensated part because magneticmetal element of Fe content reduces the decline of the ferritic saturation induction density that causes.In ferrite, A position and ion magnetic moment orientation on the B position are arranged anti-parallel mutually, and ferritic Net magnetic moment derives from the poor of magnetic moment on A, the B position, nonmagnetic Zr ⁴⁺Replaced the Fe that A is ³⁺, make the difference of magnetic moment of A, B position further strengthen, promptly improved Net magnetic moment, improved ferritic saturation induction density.Summarize described, Zr ⁴⁺And Ni ²⁺Mix resistivity and the saturation induction density that improves Mn-Zn ferrite.

In addition, the invention still further relates to the nano-crystalline MnZn ferrite material preparation method with high saturated magnetic induction and high resistivity, this preparation method comprises the steps:

(1) according to chemical formula Mn _xZn _1xFe _2-y-zNi _yZr _zO ₄The mol ratio of Mn, Zn, Fe, Ni, Zr takes by weighing MnCl in (wherein 0.2≤x≤0.9,0.1≤y≤0.4,0.1≤z≤0.3) ₂4H ₂O, ZnCl ₂4H ₂O, FeCl ₃6H ₂O, NiCl ₂6H ₂O, ZrOCl ₂8H ₂O joins in the deionized water, is heated to 50～70 ℃ and even with magnetic stirrer;

(2) in mixed solution, add ammoniacal liquor, regulate pH value to 11～12 and carry out co-precipitation;

(3) isolate throw out and several all over removing impurity with deionized water and dehydrated alcohol cleaning;

(4) cleaned throw out is put into baking oven, under 100 ℃ of temperature, dewater;

(5) moulding: use the desktop electric tabletting machine powder to be pressed into the blank of specified shape size;

(6) sintering: blank is put into resistance furnace carry out sintering processes, 700 ℃～900 ℃ of sintering temperatures, soaking time 6～10h.

The present invention compared with prior art has following advantage:

(1) adding of Ni and Zr has changed the distribution and the electromagnetic property of atom in the MnZn ferrospinel structure in the composition of the present invention, thereby has guaranteed the characteristic of MnZn ferrite high-saturation magnetic induction and high conductivity from microtexture.

(2) preparation method of the present invention is not only with low cost, technology is simple, production efficiency is high but also the sintering temperature less energy-consumption is little, helps realizing large-scale industrialization.

Description of drawings

The present invention is further detailed explanation below in conjunction with the drawings and specific embodiments.

Accompanying drawing is a nano-crystalline MnZn ferrite preparation method's of the present invention schema.

Embodiment

Shown in the drawings is preparation method's of the present invention schema.

Embodiment 1

(1) chemical formula Mn _xZn _1-xFe _2-y-zNi _yZr _zO ₄In get x=0.55, y=0.1, z=0.3 is according to mol ratio 55: 45: 160: respectively take by weighing MnCl at 10: 30 ₂4H ₂O (its purity is 99%), ZnCl ₂4H ₂O (its purity is 99%), FeCl ₃6H ₂O (its purity is 99%), NiCl ₂6H ₂O (its purity is 99%), ZrOCl ₂8H ₂O (its purity is 99%) joins in the deionized water, is heated to 50 ℃ and even with magnetic stirrer;

(2) in mixed solution, add ammoniacal liquor, regulate pH value to 11 and carry out co-precipitation;

(3) isolate throw out and clean several 5～6 removal impurity with whizzer with deionized water and dehydrated alcohol;

(4) cleaned throw out is put into baking oven, under 100 ℃ of temperature, dewater;

(5) moulding: use the desktop electric tabletting machine powder to be pressed into the cylinder shape magnet ring blank of Φ 30mm * Φ 25mm * 6mm;

(6) sintering: blank is put into resistance furnace carry out sintering processes, 700 ℃ of sintering temperatures, soaking time 10h.

Embodiment 2

(1) chemical formula Mn _xZn _1-xFe _2-y-zNi _yZr _zO ₄In get x=0.2, y=0.4, z=0.2 is according to mol ratio 10: 80: 140: respectively take by weighing MnCl at 40: 20 ₂4H ₂O (its purity is 99%), ZnCl ₂4H ₂O (its purity is 99%), FeCl ₃6H ₂O (its purity is 99%), NiCl ₂6H ₂O (its purity is 99%), ZrOCl ₂8H ₂O (its purity is 99%) joins in the deionized water, is heated to 70 ℃ and even with magnetic stirrer;

(2) in mixed solution, add ammoniacal liquor, regulate pH value to 11 and carry out co-precipitation;

(3) isolate throw out and clean several 5～6 removal impurity with whizzer with deionized water and dehydrated alcohol;

(4) cleaned throw out is put into baking oven, under 100 ℃ of temperature, dewater;

(5) moulding: use the desktop electric tabletting machine powder to be pressed into the cylinder shape magnet ring blank of Φ 30mm * Φ 25mm * 6mm;

(6) sintering: blank is put into resistance furnace carry out sintering processes, 900 ℃ of sintering temperatures, soaking time 6h.

Embodiment 3

(1) chemical formula Mn _xZn _1-xFe _2-y-zNi _yZr _zO ₄In get x=0.9, y=0.3, z=0.1 is according to mol ratio 70: 30: 160: respectively take by weighing MnCl at 30: 10 ₂4H ₂O (its purity is 99%), ZnCl ₂4H ₂O (its purity is 99%), FeCl ₃6H ₂O (its purity is 99%), NiCl ₂6H ₂O (its purity is 99%), ZrOCl ₂8H ₂O (its purity is 99%) joins in the deionized water, is heated to 60 ℃ and even with magnetic stirrer;

(2) in mixed solution, add ammoniacal liquor, regulate pH value to 12 and carry out co-precipitation;

(3) isolate throw out and clean several 5～6 removal impurity with whizzer with deionized water and dehydrated alcohol;

(4) cleaned throw out is put into baking oven, under 100 ℃ of temperature, dewater;

(5) moulding: use the desktop electric tabletting machine powder to be pressed into the cylinder shape magnet ring blank of Φ 30mm * Φ 25mm * 6mm;

(6) sintering: blank is put into resistance furnace carry out sintering processes, 800 ℃ of sintering temperatures, soaking time 8h.

Detect the crystalline structure of embodiment 1,2,3 with XRD, and estimate grain-size with the Scherrer formula; Measure the electricalresistivity of embodiment 1,2,3 ferrites 25 ℃ the time with the four point probe resistivity tester; Measure the saturation induction density B of embodiment 1,2,3 ferritic 25 ℃ the time with the vibrating sample magnetometer that has high-temperature control platform annex _sShown in the measurement result table 1.

As can be seen from Table 1, soft magnetic ferrite of the present invention has high resistivity and high saturated magnetic induction, and the magnetic core made from it can be widely used in communicating by letter, in the devices such as various types of inducers, transformer, reactance coil, suppressor and wave filter in broadcasting, TV, control automatically, spationautics, computer technology, electronics and other IT industry.

Table 1

The foregoing description does not limit the present invention in any way, and every employing is equal to replaces or technical scheme that the mode of equivalent transformation obtains all drops in protection scope of the present invention.

Claims (2)

1. the nano-crystalline MnZn ferrite material of high saturated magnetic induction and high resistivity, its chemical formulation is: Mn _xZn _1-xFe _2-y-zNi _yZr _zO ₄, 0.2≤x≤0.9,0.1≤y≤0.4,0.1≤z≤0.3 wherein.

2. the nano-crystalline MnZn ferrite material preparation method of high saturated magnetic induction and high resistivity is characterized in that this preparation method comprises the steps:

(1) according to chemical formula Mn _xZn _1-xFe _2-y-zNi _yZr _zO ₄, 0.2≤x≤0.9,0.1≤y≤0.4,0.1≤z≤0.3 wherein, the mol ratio of Mn, Zn, Fe, Ni, Zr takes by weighing MnCl in the described chemical formula ₂4H ₂O, ZnCl ₂4H ₂O, FeCl ₃6H ₂O, NiCl ₂6H ₂O, ZrOCl ₂8H ₂O joins in the deionized water, is heated to 50～70 ℃ and even with magnetic stirrer;

(2) in mixed solution, add ammoniacal liquor, regulate pH value to 11～12 and carry out co-precipitation;

(3) isolate throw out and several all over removing impurity with deionized water and dehydrated alcohol cleaning;

(4) cleaned throw out is put into baking oven, under 100 ℃ of temperature, dewater;

(5) moulding: use the desktop electric tabletting machine powder to be pressed into the blank of specified shape size;

(6) sintering: blank is put into resistance furnace carry out sintering processes, 700 ℃～900 ℃ of sintering temperatures, soaking time 6～10h.