KR20090061555A - A nicuzn ferrite and its manufacturing methods thereof - Google Patents

Abstract

A NiCuZn ferrite and a manufacture method thereof are provided to show relatively high initial permeability in a wide temperature range and high saturation flux density with high Curie temperature. A NiCuZn ferrite is composed of a main component and a minor component. The main component indicates ferric oxide, nickel monoxide, zinc oxide and copper oxide. More particularly, the main component comprises 48mol%-50mol% of Fe2O3, 13mol%-16mol% of NiO, 29mol%-31.5mol% of ZnO and 4.5mol%-6.5mol% of CuO. The minor component contains vanadium oxide, molybdenum oxide and titanium oxide. The total content of the minor components is 0.01wt%-0.08wt% on the basis of the total content of the main components. The minor components are converted to V2O5, MoO3 and TiO2 respectively.

Description

A kind of nickel copper zinc ferrite and its manufacturing method {A NiCuZn ferrite and its manufacturing methods}

The present invention relates to a kind of nickel zinc ferrite and a method of manufacturing the same, and more particularly, the present invention relates to a kind of high magnetic flux density, high Curie temperature, relatively high permeability, low loss nickel copper zinc ferrite and a method of manufacturing the same.

Among many electrical equipments, transformers occupy a very large area, and the electrical energy consumption of transformers accounts for most of the static consumption of electrical equipment. In view of the volume and electrical energy of transformers, soft magnetic ferrite magnetic material plays an important role among them. It's happening. As electronic equipment such as power transformers, office automation, and telecommunications develop into thinner, lighter, smaller, more mobile, integrated, and multifunctional systems, the market demand for transformers with smaller volume and higher efficiency will increase. Therefore, ferrite magnetic materials with high overall performance such as high wave count, relatively wide temperature range, high permeability, high saturation magnetic flux density, high Curie temperature, high resistance and low porosity loss will be indispensable among them. It has become more and more extensive and widespread.

For example, color television, which continues to be a leading player in consumer electronics products in China, will be the world's largest producer of 200 million units, reaching 200 million units in 2010. Among them, China's production volume is 80.83 million, and will exceed 100 million by 2010. Future development direction will be excessive due to high definition, big screen and digitalization, and flat TV will occupy about 60%. This trend puts stricter demands on magnetic material products as follows. 1. High quality: Power transformer power should be stable, material power loss is small and magnetization strength should be large. 2. The image should be warm and clear: High permeability materials, soft magnetic cores to prevent electromagnetic interference, and high performance light collecting panels are required. 3. Digital development: The demand for power loss, permeability, and frequency of use of soft magnetic materials are all higher than that of simulation. 4. High frequency division: Requires ferrite magnetic cores to have a relatively high working frequency. 5. Low Power Loss: The International Energy Department is required to reduce the standby power of color television to 1 watt, thus submitting a new demand for lower power loss for ferrite materials. Therefore, the DC-DC converter which converts the DC voltage supplied by the battery to the DC voltage required by the electric circuit, and the DC-AC inverter used for the liquid crystal backlight high voltage AC voltage must reduce the magnetic loss of the ferrite magnetic core among them. It has to reach the goal of reducing the heat generation of electronic equipment and greatly saving energy.

In general, soft magnetic ferrite materials are mainly manganese zinc ferrite and nickel zinc ferrite. Among them, manganese zinc ferrite has higher saturation magnetic flux density Bs, higher initial magnetic permeability μi and lower loss than nickel zinc ferrite. However, because the grain structure of manganese zinc material is dense, the resistivity is generally 10 ⁶ Ωm, and the magnetization process is based on the movement of the magnetic walls. In the trend of miniaturization and high frequency of electronic equipments, magnetic cores of sensitive components easily break down high voltage with adjacent copper wires. Therefore, a very large insulation distance must be guaranteed between the core and coil terminals and lead wires, or strict insulation measures can be used to ensure the necessary insulation withstand voltage, which inevitably increases the volume of the transformer. On the contrary, nickel zinc material belongs to porous fine grain structure and its resistivity is high, so it is generally 10 ⁷ Ωm quantity class. The magnetization process is based on magnetization rotation, and when the magnetization rotation is focused, natural resonance occurs under high frequency. In addition to high resistivity, the application frequency range is higher than that of manganese zinc. If the nickel zinc ferrite with resistivity is more than 10 ⁷ Ωm, the above insulation and breakdown voltage problem can be easily solved. However, nickel sinter ferrite materials with relatively high Curie temperature have very low saturation magnetic flux density Bs and ultra-permeability μi. In addition, the core loss is relatively high. Therefore, any of the above-mentioned two magnetic cores of the ferrite material, which are related to the frequency converter core of the transformer, especially the liquid crystal backlight, which has a very high output voltage in some electronic equipments, will practically meet the demand for miniaturization, aggregation, multifunction, and high frequency generation. Can't satisfy

In the above-mentioned related fields, a type of magnetic ferrite material has been disclosed in a Japanese patent application document with publication number JP2003-300774A, which contains the following main components. When iron oxide is converted into Fe ₂ O ₃ , its content is in the range of 48.5-50.5 mol%, when copper oxide is converted into CuO, the content is in the range of 3-12 mol%, and zinc oxide is in the range of 24-36 mol% when converted into ZnO. the rest of the nickel monoxide and subcomponent is a V ₂ O ₅ is less than 0.15wt%. This magnetic ferrite material has a minimum magnetic core power loss within the temperature range of 20-140 ℃, the minimum magnetic core loss measured at 50kHz and 150mT is 250kW / m ³ or less and the saturation magnetic flux density is 300mT or more.

In addition, a Chinese patent application document with the application number CN200510060652.5 discloses a kind of high initial permeability, low loss nickel zinc ferrite material and a method of manufacturing the same. When the main component of this ferrite is calculated as an oxide, 40-50 mol% of Fe ₂ O ₃ , NiO 10 a -18mol%, ZnO 30-38mol%, CuO 0-10mol%, the secondary component _{V 2 O 5 0-1wt%, Mo} 2 O 3 0-0.5wt%. The invention has an initial permeability of more than 2500, a specific loss factor of less than 20 * 10 ^-6 (100KHz), a specific temperature coefficient of less than 4 * 10 ^-6 / ℃ (25-65 ℃), and a Curie temperature of more than 100 ℃. It is said that high permeability nickel zinc ferrite materials can be produced.

However, the overall performance of the above-described ferrite materials manufactured in the prior art cannot truly propel electronic equipment to develop in miniaturization, mobility, aggregation, and multifunctionalization.

SUMMARY OF THE INVENTION In order to overcome the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a kind of nickel copper zinc ferrite and a method of manufacturing the same, and the nickel copper zinc ferrite should have excellent comprehensive performance as follows. It has higher Curie temperature and has relatively high super-permeability, high saturation flux density, and relatively low loss over a relatively wide temperature range, so that the electronic equipment can be truly developed in the direction of miniaturization, mobility, aggregation, and multifunction. It is to let.

Thus, one of the technical solutions of the present invention is a kind of nickel copper zinc ferrite, which contains a main component and a subcomponent. The main components are iron oxide, nickel monoxide, zinc oxide, and copper oxide, respectively. The main components described above are calculated by their standard, and the content is Fe ₂ O ₃ : 48mol% -50mol%, NiO: 13mol% -16mol%, ZnO: 29mol% -31.5 mol%, CuO: 4.5 mol%-6.5 mol%. The subcomponents described above include vanadium oxide, molybdenum oxide, and titanium oxide. The subcomponents described above are 0.01wt% -0.08wt% based on the respective standards V ₂ O ₅ , MoO ₃ , TiO ₂ .

Experiments have demonstrated that the present invention is uniform in size of grains using a suitable formulation (e.g., average size control of milling sanding, control of sintering curve and warming temperature, etc.) suitable for complex mixing of rational ingredients and optimized miscellaneous materials. Nickel copper zinc ferrite was manufactured with no ideal crystal grains and excellent aesthetic structure. The nickel copper zinc ferrite magnetic core has a relatively high Curie temperature and a relatively wide working temperature range, and greatly improved permeability and saturation magnetic flux density. Power loss is relatively low. Specifically, the present invention produced a magnetic core with a Curie temperature higher than 160 ° C., and its initial permeability was greatly improved to 1200 ± 20% (100KHz, 0.1V, 25 ° C. ± 3 ° C.), and also 50KHz, 150 mT, 20 ° C. porosity loss minimum value in the temperature zone -140 ℃ is 250kW / m ³ or less and the saturation magnetic flux density at H = 1600A / m, 25 ℃ ± 3 ℃ not less than 360mT. The magnetic core comprehensive performance of the present invention is excellent, and the performance such as ultra-permeability, saturation magnetic flux density, power loss, resistivity, etc. can all satisfy the power generation demand of various electronic equipment. Since the Curie temperature of the magnetic core of the present invention is relatively high, for example, the Curie temperature of the magnetic core of the present invention is still high even though the heat generation of the magnetic core is 80-100 ° C. even higher due to the temperature of the work and the environment among the miniaturized, mobile, integrated, and multifunctionalized electronic equipment. Much lower and does not affect the other performance of the present invention. Thus, the magnetic core of the present invention can be substantially employed in electronic equipment of miniaturization, mobileization, aggregation, and multifunctionalization, and can greatly promote miniaturization, mobility, aggregation, and multifunctionalization of electronic equipment.

The experiment is limited to the main component of the present invention on the basis of selecting the subcomponent and limiting the subcomponent content is as follows. Fe ₂ O ₃ : If less than 48 mol%, the magnetic core loss is large, and if it exceeds 50 mol%, the resistance is rapidly reduced. NiO: If it is less than 13 mol%, the permeability is low. If it exceeds 16 mol%, the cost is high and the loss is high. ZnO: If less than 29 mol%, the permeability is low and if it exceeds 31.5 mol%, the Curie temperature is lowered. CuO: If less than 4.5 mol%, the sintering temperature is high to form an ideal grain, and if it exceeds 6.5 mol%, the Curie temperature is lowered. In addition, if the sub-component is too high, said low temperature is easy also form pores is easy to produce the spinel phase under the size of the crystal grains not uniform, subcomponent a is too small in the CuO as nucleation Cu ^{2 +} can enter the whole grid It is heterogeneous.

The nickel copper zinc ferrite of the present invention also includes the following specific details.

The subcomponents described above are calculated by the standards V ₂ O ₅ , MoO ₃ and TiO ₂ , respectively, and the content is V ₂ O ₅ : 0.004wt% -0.03wt%, MoO ₃ : 0.003wt% -0.02wt%, TiO ₂ : 0.003wt% -0.03wt%.

The subcomponents described also include one or more of manganese oxide, Bi ₂ O ₃ , Nb ₂ O ₅ .

The manganese oxide described above is added in the form of manganese carbonate, and the added amount of the subcomponents relative to the total amount of the main components described above are manganese carbonate: 0.01wt% -0.8wt%, Bi ₂ O ₃ : 0wt% -0.02wt% ， Nb ₂ O ₅ : 0 wt%-0.04wt%.

The Curie temperature Tc of the nickel copper zinc ferrite described above is not lower than 160 ° C, the super-permeability μi is 1200 ± 20% at room temperature, the saturation magnetic flux density Bs is not lower than 360 mT and the resistivity is not lower than 10 ⁷ Ωm.

Correspondingly, another technical solution of the present invention is a method of producing nickel copper zinc ferrite as described above, which method in turn includes the following steps.

A. Four main components Fe ₂ O ₃ , NiO, ZnO, CuO particles are mixed and then first sanded to prepare a main powder.

B. After drying and pre-firing the above-mentioned main ingredient powder, add water, dispersant and subcomponents, and then carry out the second sanding together. Prepare μm of mixed flour.

C. The mixed powder is dried and pressed to make a blank. The blank is placed in an air kiln and sintered at a temperature of 1030 ° C.-1110 ° C. for 2 hours to 6 hours, followed by cooling to prepare a nickel copper zinc ferrite product.

Experimental proved that the nickel copper zinc ferrite powder produced by the production method of the present invention has excellent molding performance and sintered products can reach the expected technical indicators.

The production method of the present invention further includes the following specific details.

The drying process described in step B described above employs a spraying method and the prefiring temperature described is 830 ° C-910 ° C.

The blank density produced by the press molding as described in step C described above is 3.20 ± 0.20 g / cm ³ .

The production method described above includes adding manganese carbonate to the above described main ingredient powder, and the addition of manganese proceeds before sanding or during the sanding process in steps A and B described above.

The primary addition amount of manganese carbonate described is 2-3 times the secondary addition amount, and the particle average diameter of the main component powder described in step A described above is controlled to 1.00 μm ± 0.20 μm.

Nickel copper zinc ferrite of the present invention has a higher Curie temperature, relatively high initial permeability, high saturation magnetic flux density, and low loss in a relatively wide temperature range, thus miniaturizing, mobilizing, converging, and multifunctional electronic equipment. It can better meet the demands of comprehensive performance.

Hereinafter, the present invention will be described in further detail with reference to specific examples.

Example 1

49.5 mol% Fe ₂ O ₃ , 14.3 mol% NiO, 30.2 mol% ZnO, 6.0 mol% CuO. After mixing the above-mentioned raw materials, put them together in a sanding machine and proceed with stirring, while controlling the average diameter of the particles to 1.00μm ± 0.20μm, and after preliminary spraying, put them in an electrothermal rotary kiln at 880 ℃ ± 10 ℃ and proceed with prefiring. do. Then, the prefired material is placed in a sanding machine and subjected to the second sanding. During the sanding process, water, a dispersant, and an antifoaming agent are added, and an additive is added, but the weight ratio of each substance in the additives described in relation to the total amount of the main components described. Are 0.01 wt% of V ₂ O _5, 0.01 wt% of MoO ₃ , and 0.02 wt% of TiO ₂ , respectively, and control the average diameter φ of the particles during sanding to 1.00 μm ± 0.10 μm. Afterwards, secondary spraying is performed to prepare nickel copper zinc ferrite powder.

Take this powder and pressurize it with annular magnetic core of φ25mm × φ15mm × 7.5mm. Molding density is 3.20 ± 0.20g / cm ³ and sintering at 1050 ℃ ± 10 ℃ in air kiln for 4 hours-5 hours. Cool.

Magnetic cores manufactured through the above-described process were measured using a magnetic core such as a US 2330 power meter, an HP4284 inductance meter, a constant temperature box, and the like.

Example 2 ：

The compounding ratio and the crafting procedure are the same as those of Example 1, and the sub-components also contain MnCO ₃ : 0.60wt% and add twice, 0.45wt% in the first sanding and 0.15wt in the second sanding Add%

Example 3 ：

49.0 mol% Fe ₂ O ₃ , 14.6 mol% NiO, 30.4 mol% ZnO, 5.6 mol% CuO. After mixing the above-mentioned raw materials, put them together in a sanding machine and proceed with stirring, while controlling the average diameter of the particles to 1.00μm ± 0.20μm, and after preliminary spraying, put them in an electrothermal rotary kiln at 890 ℃ ± 10 ℃ and proceed with prefiring. do. Then, the prefired material is placed in a sanding machine and subjected to the second sanding. During the sanding process, water, a dispersant, an antifoaming agent is added, and an additive is added, but the weight ratio of each substance in the additives described in relation to the total amount of the main components described. The contents are 0.02 wt% of V ₂ O ₅ , 0.018 wt% of MoO ₃ , 0.01 wt% of TiO ₂ , and 0.02% of Bi ₂ O _3. The average diameter of the particles during sanding is controlled to 0.95 μm ± 0.1 μm. Afterwards, secondary spraying is performed to prepare nickel copper zinc ferrite powder.

Take this powder and pressurize it with a ring-shaped magnetic core of φ25mm × φ15mm × 7.5mm. Molding density is 3.20 ± 0.20g / cm ³ and sintering in air kiln at 1080 ℃ ± 10 ℃ for 3-4 hours. Cool.

Example 4 ：

The compounding ratio and the crafting procedure are the same as in Example 3, and the sub-components also contain 0.40 wt% of MnCO ₃ and are added twice, adding 0.28 wt% for the first sanding and 0.12 wt% for the second sanding. Add. At the same time, 0.013 wt% of Nb ₂ O ₅ is added on the basis of Example 3 during the second sanding.

Example 5 ：

Take 48.8 mol% Fe ₂ O ₃ , 15.1 mol% NiO, 30.7 mol% ZnO, 5.4 mol% CuO. After mixing the above-mentioned raw materials, put them together in a sanding machine and proceed with stirring, while controlling the average diameter of the particles to 1.00μm ± 0.20μm, and after preliminary spraying, put them in an electrothermal rotary kiln at 860 ℃ ± 10 ℃ and proceed with prefiring. do. Then, the prefired material is placed in a sanding machine and subjected to the second sanding. During the sanding process, water, a dispersant, an antifoaming agent is added, and an additive is added, but the weight ratio of each substance in the additives described in relation to the total amount of the main components described. The content is 0.015wt% of V ₂ O ₅ , 0.01wt% of MoO _3, 0.01wt% of TiO ₂ , 0.02 wt% of Nb ₂ O ₅ and the average diameter of the particles during sanding is controlled to 0.90μm ± 0.10μm. Afterwards, secondary spraying is performed to prepare nickel copper zinc ferrite powder.

Take this powder and pressurize it with a ring-shaped magnetic core of φ25mm × φ15mm × 7.5mm. Molding density is 3.20 ± 0.20g / cm ³ and sintering in air kiln at 1080 ℃ ± 10 ℃ for 3-4 hours. Cool.

Magnetic cores manufactured through the above-described process were measured using a magnetic core such as a US 2330 power meter, an HP4284 inductance meter, a constant temperature box, and the like.

The present invention annular magnetic core material performance Item Example 1 Example 2 Example 3 Example 4 Example 5 Ultra Permeability μi (100kHz, 0.1V, 10Ts) 25 ℃ 1250 1350 1200 1180 1205 Saturated Magnetic Flux Density Bs (mT) H = 1600A / m 25 ℃ 367 373 370 369 375 Power Loss Pv (kW / m ³ ) (100kHz, 200mT) 25 ℃ 300 290 310 320 328 100 ℃ 240 230 240 250 256 120 ℃ 260 250 270 280 275 Curie temperature Tc （℃） 165 165 162 162 163 Resistivity （Ωm） 2 × 10 ⁷ 1.8 × 10 ⁷ 2 × 10 ⁷ 1.8 × 10 ⁷ 1.9 × 10 ⁷ Specific loss factor tanθ / μi (100kHz, 0.1V, 10Ts, 25 ℃) 12 x 10 ^-6 14 x 10 ^-6 10 x 10 ^-6 8 x 10 ^-6 7 × ^10-6

As shown in Table 1, the nickel copper zinc ferrite of the present invention has significantly improved the initial permeability μi and the saturation magnetic flux density Bs at a very high Curie temperature and a wider working temperature range, and has a minimum porosity loss within the temperature range of 25 ° C to 120 ° C. 250 kW / m ³ or less. This self-contained frequency converter can meet the needs of comprehensive performance for further miniaturizing, mobilizing, integrating, and multifunctionalizing many liquid crystal backlights.

Claims (10)

It is about a kind of nickel copper zinc ferrite, The ferrite includes a main component and a subcomponent, and the main components are iron oxide, nickel monoxide, zinc oxide, and copper oxide, respectively. The characteristics of the ferrite are calculated by using the standard components of Fe ₂ O ₃ : 48mol% -50mol%, NiO : 13 mol%-16 mol%, ZnO: 29 mol%-31.5 mol%, CuO: 4.5 mol%-6.5 mol% The subcomponents mentioned include vanadium oxide, molybdenum oxide, and titanium oxide, and are described with respect to the total amount of the principal component described. Nickel copper zinc ferrite, characterized in that the total content is 0.01wt% -0.08wt% when the subcomponents are calculated by the standard V ₂ O ₅ , MoO ₃ , TiO ₂ . In claim 1, The subcomponents were calculated as the standards V ₂ O ₅ , MoO ₃ and TiO ₂ , respectively, and the contents thereof were V ₂ O ₅ : 0.004 wt% -0.03 wt%, MoO ₃ : 0.003 wt%-0.02 wt%, and TiO ₂ : Nickel copper zinc ferrite, characterized in that 0.003wt% -0.03wt%. In claim 1 or 2, The copper sub-component nickel nickel zinc ferrite, characterized in that it further comprises one or more of manganese oxide, Bi ₂ O ₃ , Nb ₂ O ₅ . In claim 3, The manganese oxide is added in the form of manganese carbonate, and the added amount of the sub-component described relative to the total amount of the main component described above is manganese carbonate: 0.01wt% -0.8wt%, Bi ₂ O ₃ : 0wt% -0.02wt%, Nb ₂ O ₅ : Nickel copper zinc ferrite, which is 0 wt% -0.04wt%. In claim 1, The Curie temperature Tc of the nickel copper zinc ferrite is not lower than 160 ° C., at room temperature, the initial permeability μi is 1200 ± 20%, the saturation magnetic flux density Bs is not lower than 360 mT, and the resistivity is not lower than 10 ⁷ Ωm. ferrite. It relates to a method for producing nickel copper zinc ferrite described in claim 1-5, which includes the following steps in order. A. Four main components Fe ₂ O ₃ , NiO, ZnO, CuO particles are mixed and then first sanded to prepare a main powder. B. After drying and prefiring the above-mentioned main ingredient powder, add water, dispersant and subsidiary ingredients, and then carry out the second sanding together, add the adhesive and the antifoaming agent during the second sanding process, and the average diameter of the particles is 0.60μm-1.20. Prepare μm of mixed flour. C. The mixed powder is dried and pressed to make a blank. The blank is placed in an air kiln and sintered at a temperature of 1030 ° C.-1110 ° C. for 2 hours to 6 hours, followed by cooling to prepare a nickel copper zinc ferrite product. . In claim 6, In the method for producing nickel copper zinc ferrite described above, the drying process described in step B described above employs a spraying method, and the prefiring temperature described is 830 ° C-910 ° C. Manufacturing method. In claim 6, The blank density produced by the pressing molding described in the step C is 3.20 ± 0.20 g / cm ³ The production method of nickel copper zinc ferrite. In claim 6, And adding manganese carbonate to the main ingredient powder, wherein the addition of manganese carbonate is carried out before sanding or during sanding in steps A and B, respectively. In claim 9, The primary addition amount of the manganese carbonate is 2-3 times the secondary addition amount, the nickel copper zinc ferrite, characterized in that to control the particle average diameter of the main component powder described in step A described above to 1.00μm ± 0.20μm Manufacturing method.