CN115925405A - NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature and preparation method thereof - Google Patents

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.

一种高磁导率高居里温度NiCuZn软磁铁氧体材料及其制备方法A kind of NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature and preparation method thereof

技术领域technical field

本发明涉及软磁铁氧体电子信息材料技术领域，具体涉及一种高磁导率高居里温度NiCuZn软磁铁氧体材料及其制备方法。The invention relates to the technical field of soft ferrite electronic information materials, in particular to a NiCuZn soft ferrite material with high magnetic permeability and high Curie temperature and a preparation method thereof.

背景技术Background technique

NiCuZn软磁铁氧体材料作为一种非常重要的电子信息材料，在通信、电子、航空航天、军事科技等领域有着非常广泛的应用，它具有高的电阻率ρ、高截止频率、高初始磁导率μ_i、低损耗、低温度系数等优点，可广泛应用于高频电感磁芯、近场通信(NFC)系统、叠层片式电感器(MLCI)及抗EMI器件等。现有的NiCuZn软磁铁氧体材料初始磁导率大多低于1600，而且NiCuZn软磁铁氧体材料一般磁导率越高其居里温度(T_c)越低，如：初始磁导率大于1500、室温饱和磁通密度大于250mT的NiZn系列材料T_c约为100℃，具有较高T_c的NiZn系列材料其磁导率通常均小于1000。低T_c意味着材料的工作温度范围越窄，限制了其在诸多领域的应用。As a very important electronic information material, NiCuZn soft magnetic ferrite material has a very wide range of applications in the fields of communication, electronics, aerospace, military technology, etc. It has high resistivity ρ, high cut-off frequency, high initial permeability It can be widely used in high-frequency inductor cores, _near -field communication (NFC) systems, multilayer chip inductors (MLCI) and anti-EMI devices. The initial permeability of existing NiCuZn soft ferrite materials is mostly lower than 1600, and the higher the permeability of NiCuZn soft ferrite materials, the lower the Curie temperature (T _c ), for example: the initial permeability is greater than 1500 1. The T _c of NiZn series materials with room temperature saturation magnetic flux density greater than 250mT is about 100°C, and the magnetic permeability of NiZn series materials with higher T _c is usually less than 1000. Low _Tc means that the working temperature range of the material is narrower, which limits its application in many fields.

CN 101236819A公开了一种镍铜锌铁氧体及其制造方法，该铁氧体包含主成分和副成分，所述主成分按摩尔百分比计算：Fe₂O₃：48mol％～50mol％，NiO：13mol％～16mol％，ZnO：29mol％～31.5mol％，CuO：4.5mol％～6.5mol％；所述副成分包括氧化钒、氧化钼、氧化钛，副成分的填加总含量为0.01wt％～0.08wt％。所制备得到的镍铜锌铁氧体材料初始磁导率(μ_i)1200±20％，T_c不低于160℃，饱和磁通密度不低于360mT。CN 101236819A discloses a nickel-copper-zinc ferrite and its manufacturing method. The ferrite contains a main component and an auxiliary component. The main _component is calculated by mole percentage: _Fe2O3 : 48mol%-50mol%, NiO: 13mol%～16mol%, ZnO: 29mol%～31.5mol%, CuO: 4.5mol%～6.5mol%; the subcomponents include vanadium oxide, molybdenum oxide, titanium oxide, and the total content of subcomponents is 0.01wt% ~0.08 wt%. The prepared nickel-copper-zinc ferrite material has an initial magnetic permeability (μ _i ) of 1200±20%, a _Tc not lower than 160°C, and a saturation magnetic flux density not lower than 360mT.

CN 104030669A公开了一种NiZn铁氧体的压滤成型的制备方法。主成分以摩尔百分比为：Fe₂O₃：48～54mol％、ZnO：30～32mol％、NiO：3.5～10mol％、CuO：8～15mol％；掺杂剂按重量百分比计算：V₂O₅：0～3wt％。所获得的最优磁性能如下：μ_i为2100，比损耗系数的倒数为5×10⁴，T_c为98℃，饱和磁通密度240mT。CN 104030669A discloses a method for preparing NiZn ferrite by filter press molding. The main components are: Fe ₂ O ₃ : 48-54 mol%, ZnO: 30-32 mol%, NiO: 3.5-10 mol%, CuO: 8-15 mol%; the dopant is calculated by weight percentage: V ₂ O ₅ : 0~3wt%. The obtained optimal magnetic properties are as follows: μ _i is 2100, the reciprocal of the specific loss coefficient is 5×10 ⁴ , T _c is 98°C, and the saturation magnetic flux density is 240 mT.

CN 109320227A公开了一种NiCuZn铁氧体材料及其制备方法和用途。所述NiCuZn铁氧体材料主要由Fe₂O₃、ZnO、NiO和CuO组成，以NiCuZn铁氧体材料的总摩尔量为100％计，Fe₂O₃的摩尔百分数为48.8～50mol％，ZnO的摩尔百分数为32～34mol％，NiO的摩尔百分数为6.5～8mol％，CuO的摩尔百分数为8.5～12.7mol％。所制备得到的NiCuZn铁氧体材料在100～300kHz范围内，复数磁导率的实部μ′为1600～2000和虚部μ″不大于50，100kHz、1194A/m、25℃下饱和磁感应强度Bs≥240mT和矫顽力H_c≤60A/m，居里温度T_c为95～110℃。CN 109320227A discloses a NiCuZn ferrite material and its preparation method and application. The NiCuZn ferrite material is mainly composed of Fe ₂ O ₃ , ZnO, NiO and CuO, the molar percentage of Fe ₂ O ₃ is 48.8-50 mol% based on the total molar weight of the NiCuZn ferrite material as 100%, and the ZnO The mole percentage of NiO is 32-34 mol%, the mole percentage of NiO is 6.5-8 mol%, and the mole percentage of CuO is 8.5-12.7 mol%. The prepared NiCuZn ferrite material is within the range of 100-300kHz, the real part of the complex permeability μ' is 1600-2000 and the imaginary part μ" is not more than 50, and the saturation magnetic induction is at 100kHz, 1194A/m, and 25°C Bs≥240mT and coercive force _Hc≤60A /m, Curie temperature _Tc is 95～110℃.

上述公开的专利中，有些是初始磁导低、有些是居里温度低、还有些是饱和磁通密度较低，很难达到同时具有高的初始磁导率、高居里温度及高饱和磁通密度。存在的这些问题使其无法满足微型高品质电感器、脉冲变压器、电磁干扰抑制器等对软磁材料的使用要求。且随着电子产品小型化、高功率化、宽温化的发展趋势，对电子元器件提出了更高要求，这就要求NiCuZn软磁铁氧体材料不仅具有高的初始磁导率和高的居里温度，而且还要保证其具有耐受大电流、低损耗等特点。而目前的NiCuZn软磁铁氧体材料和制造工艺已经无法满足上述要求。Among the above disclosed patents, some have low initial magnetic permeability, some have low Curie temperature, and some have low saturation magnetic flux density. It is difficult to achieve high initial magnetic permeability, high Curie temperature and high saturation magnetic flux at the same time. density. These problems make it impossible to meet the requirements for the use of soft magnetic materials such as miniature high-quality inductors, pulse transformers, and electromagnetic interference suppressors. And with the development trend of miniaturization, high power and wide temperature of electronic products, higher requirements are put forward for electronic components, which requires NiCuZn soft magnetic ferrite materials not only to have high initial permeability and high In addition, it must be guaranteed that it has the characteristics of high current resistance and low loss. However, the current NiCuZn soft ferrite material and manufacturing process can no longer meet the above requirements.

发明内容Contents of the invention

为解决现有技术中存在的问题，本发明的目的在于提供一种高磁导率高居里温度NiCuZn软磁铁氧体材料及其制备方法，该材料不仅具有高的初始磁导率和高的居里温度，而且还具备高的饱和磁通密度以及更低的损耗。In order to solve the problems existing in the prior art, the object of the present invention is to provide a high magnetic permeability high Curie temperature NiCuZn soft magnetic ferrite material and its preparation method, the material not only has high initial magnetic permeability and high residence temperature, but also has a high saturation flux density and lower loss.

本发明采用的技术方案如下：The technical scheme that the present invention adopts is as follows:

一种高磁导率高居里温度NiCuZn软磁铁氧体材料，其组分包括主成分和掺杂成分，以质量百分数计，所述主成分包含有：Fe₂O₃:66.22wt％～68.65wt％；ZnO:18.30wt％～22.15wt％；NiO:7.75wt％～9.85wt％；余量为CuO；A NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature. Its components include main components and doping components. In mass percentage, the main components include: Fe ₂ O ₃ : 66.22wt% ~ 68.65wt %; ZnO: 18.30wt% ~ 22.15wt%; NiO: 7.75wt% ~ 9.85wt%; the balance is CuO;

所述掺杂成分包含Y₂O₃、MoO₃、V₂O₅和MnCO₃，其中，Y₂O₃含量为主成分质量的0.05wt％～0.10wt％，MoO₃含量为主成分质量的0.06wt％～0.18wt％，V₂O₅含量为主成分质量的0.05wt％～0.15wt％，MnCO₃含量为主成分质量的0.04wt％～0.12wt％。The doping components include Y ₂ O ₃ , MoO ₃ , V ₂ O ₅ and MnCO ₃ , wherein the Y ₂ O ₃ content is 0.05wt% to 0.10wt% of the main component mass, and the MoO ₃ content is 0.05 wt% of the main component mass 0.06wt% to 0.18wt%, the V ₂ O ₅ content is 0.05wt% to 0.15wt% of the main component mass, and the MnCO ₃ content is 0.04wt% to 0.12wt% of the main component mass.

优选的，掺杂成分的总质量不大于主成分质量的0.55wt％。Preferably, the total mass of the doping components is not greater than 0.55 wt% of the mass of the main component.

优选的，所述高磁导率高居里温度NiCuZn软磁铁氧体材料在100kHz测试频率下，初始磁导率为1665～2320，比损耗系数为13×10^-6-35.5×10^-6，居里温度为124-145℃，饱和磁通密度为329-352mT，矫顽力为18-28.5A/m。Preferably, the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature has an initial magnetic permeability of 1665-2320 at a test frequency of 100 kHz, and a specific loss coefficient of 13×10 ^-6 -35.5×10 ^-6 , ranking The inner temperature is 124-145°C, the saturation magnetic flux density is 329-352mT, and the coercive force is 18-28.5A/m.

优选的，所述高磁导率高居里温度NiCuZn软磁铁氧体材料的密度为5.17-5.37g/cm³。Preferably, the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature has a density of 5.17-5.37 g/cm ³ .

本发明如上所述的一种高磁导率高居里温度NiCuZn软磁铁氧体材料的制备方法，包括如下过程：The preparation method of a kind of high magnetic permeability high Curie temperature NiCuZn soft magnetic ferrite material of the present invention as described above, comprises following process:

将Fe₂O₃粉末、ZnO粉末、NiO粉末和CuO粉末混匀，得到混合料A；Mix _Fe2O3 powder, ZnO powder, NiO powder and CuO powder to obtain mixture A _;

对所述混合料A进行造粒并预烧，得到预烧料；The mixture A is granulated and calcined to obtain a calcined material;

将所述预烧料进行破碎处理，之后加入掺杂成分并进行球磨混匀，得到混合料B；Crushing the calcined material, then adding doping ingredients and ball milling to obtain a mixture B;

对所述混合料B进行造粒并压制成型，得到样环毛坯；The mixture B is granulated and pressed into shape to obtain a sample ring blank;

对所述样环坯体进行烧结，得到所述高磁导率高居里温度NiCuZn软磁铁氧体材料。The sample ring green body is sintered to obtain the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature.

优选的，将Fe₂O₃粉末、ZnO粉末、NiO粉末和CuO粉末混匀，得到混合料A时：Preferably, when _Fe2O3 powder, ZnO powder, NiO powder and CuO powder are mixed to obtain _the mixture A:

将Fe₂O₃粉末、ZnO粉末、NiO粉末和CuO粉末湿法混匀，湿法混匀时，钢球：超纯水：粉料的重量比为5：(1.3～1.7)：1，球磨转速为100-120转/min，湿法球磨混匀时长为3-6h；湿法混匀后，在浆料中加入PVA溶液湿法再次混磨，PVA溶液的加入量为4wt％-6wt％，加入PVA溶液后再次球磨时间为20-40min。Mix Fe ₂ O ₃ powder, ZnO powder, NiO powder and CuO powder in a wet method. When wet mixing, the weight ratio of steel ball: ultrapure water: powder is 5: (1.3～1.7): 1, and ball milling The rotation speed is 100-120 rpm, and the mixing time of wet ball milling is 3-6h; after wet mixing, add PVA solution to the slurry for wet mixing again, and the amount of PVA solution added is 4wt%-6wt% After adding the PVA solution, the ball milling time is 20-40min again.

优选的，对所述混合料A进行造粒时，造粒方法为红喷造粒，造粒过程中喷雾塔出口温度为85-95℃，进口温度为160-180℃，造粒粒径为120-180μm，预烧时，预烧温度为930-970℃，保温时间2-3h。Preferably, when the mixture A is granulated, the granulation method is red spray granulation. During the granulation process, the outlet temperature of the spray tower is 85-95°C, the inlet temperature is 160-180°C, and the granulation particle size is 120-180μm, when pre-fired, the pre-fired temperature is 930-970°C, and the holding time is 2-3h.

优选的，将所述预烧料破碎处理至280-380μm，预烧料破碎料与掺杂成分球磨混匀时，磨球∶超纯水∶料的质量比为4:(1.3-1.7):1，球磨转速为380-420转/min，球磨时间为5.5-6.5h；Preferably, the pre-sintered material is crushed to 280-380 μm, and when the pre-sintered material is ball milled and mixed with the dopant component, the mass ratio of grinding ball: ultrapure water: material is 4: (1.3-1.7): 1. The ball milling speed is 380-420 rpm, and the ball milling time is 5.5-6.5h;

预烧料破碎料与掺杂成分球磨混匀后，加入PVA溶液湿法再次球磨，PVA溶液的加入量为4wt％-6wt％，加入PVA溶液后再次球磨时间为20-40min。After ball milling and mixing the calcined crushed material and doping components, add PVA solution and wet ball mill again. The amount of PVA solution added is 4wt%-6wt%. After adding PVA solution, the time for ball milling again is 20-40min.

优选的，对所述混合料B进行造粒时，造粒方法为黑喷造粒，造粒过程中喷雾塔出口温度为80-90℃，进口温度为170-190℃，造粒粒径为70-130μm；Preferably, when the mixture B is granulated, the granulation method is black spray granulation. During the granulation process, the outlet temperature of the spray tower is 80-90°C, the inlet temperature is 170-190°C, and the granulation particle size is 70-130μm;

压制成型时，在所造粒粉中加入粒粉料重量的0.10wt％-0.14wt％的硬脂酸锌作为脱模剂，成型方式采用双向加压冷压成型，成型压力9.8-10.2MPa。During compression molding, 0.10wt%-0.14wt% zinc stearate of the weight of the granulated powder is added to the granulated powder as a release agent, and the molding method adopts two-way press cold pressing molding, and the molding pressure is 9.8-10.2MPa.

优选的，对所述样环坯体进行烧结时，采用梯度升温工艺进行烧结，采用梯度升温工艺进行烧结时：Preferably, when the sample ring body is sintered, a gradient heating process is used for sintering, and when a gradient heating process is used for sintering:

先以1.3-1.7℃/min加热至440℃-500℃，保温1.8-2.2h，然后以2.8-3.2℃/min升温至900℃，再以1.8-2.2℃/min升温至1130-1170℃，保温时间2-3h，之后自然随炉冷却，得到所述高磁导率高居里温度NiCuZn软磁铁氧体材料。First heat up to 440°C-500°C at 1.3-1.7°C/min, keep warm for 1.8-2.2h, then raise the temperature to 900°C at 2.8-3.2°C/min, then raise the temperature to 1130-1170°C at 1.8-2.2°C/min, The holding time is 2-3 hours, and then naturally cooled with the furnace to obtain the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature.

本发明具有如下有益效果：The present invention has following beneficial effects:

本发明高磁导率高居里温度NiCuZn软磁铁氧体材料最优磁性能如下：在100kHz测试频率下，初始磁导率μ_i为2011，比损耗系数为28.78×10^-6，居里温度T_c＝145℃，饱和磁通密度B_s＝352mT(10kHz，4000A/m)，矫顽力H_c＝28.41A/m。此外，本发明高磁导率高居里温度NiCuZn软磁铁氧体材料具有工作频率高、温度系数小的特点。综上可以看出，本发明高磁导率高居里温度NiCuZn软磁铁氧体材料不仅具有高的初始磁导率和高的居里温度，而且还具备更高的饱和磁通密度及低的损耗。本发明可实现小型化、高工作温度、低损耗感性器件对磁性材料的要求：高的μ_i、T_c及B_s，较低的tgδ/μ_i和H_c。The optimal magnetic properties of the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature of the present invention are as follows: at a test frequency of 100 kHz, the initial magnetic permeability μ _i is 2011, the specific loss coefficient is 28.78×10 ^-6 , and the Curie temperature T _c = 145°C, 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 permeability and high Curie temperature of the present invention has the characteristics of high operating frequency and small temperature coefficient. In summary, it can be seen that the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature of the present invention not only has high initial magnetic permeability and high Curie temperature, but also has higher saturation magnetic flux density and low loss . The invention can realize the requirements of miniaturization, high working temperature and low loss inductive devices on magnetic materials: high μ _i , T _c and B _s , and low tgδ/μ _i and H _c .

附图说明Description of drawings

图1为实施例2制备的NiCuZn软磁铁氧体样品的μ_i和tgδ随频率的变化关系；Fig. 1 is the variation relation of μ _i and tg δ of the NiCuZn soft ferrite sample prepared by embodiment 2 with frequency;

图2为实施例2制备的NiCuZn软磁铁氧体样品的μ_i随温度的变化关系；Fig. 2 is the variation relation of μ _i of the NiCuZn soft ferrite sample prepared by embodiment 2 with temperature;

图3为实施例2制备的NiCuZn软磁铁氧体样品的B-H曲线。Fig. 3 is the B-H curve of the NiCuZn soft ferrite sample prepared in Example 2.

具体实施方式Detailed ways

下面结合附图和实施例来对本发明做进一步的说明。The present invention will be further described below in conjunction with the accompanying drawings and embodiments.

本发明的整体思路如下：本发明采用的主成分包括Fe₂O₃、NiO、ZnO和CuO，这几个主成分决定了NiCuZn铁氧体材料的主要技术参数(如初始磁导率、居里温度、饱和磁通密度)。此外，本发明首次使用Y₂O₃、MoO₃、V₂O₅、和MnCO₃微量元素共掺杂技术，最大限度发挥各微量元素的有益作用及离子之间的协同作用。适量的V₂O₅掺杂可使铁氧体形成液相烧结并增加磁导率，烧结过程中形成液相有助于Y₂O₃、MoO₃、MnCO₃等微量元素进入晶界从而发挥作用，少量MoO₃的掺杂可使铁氧体晶粒尺寸增大、均匀性改善、初始磁导率增加，但也会使居里温度有小幅的下降。而Y₂O₃可影响铁氧体四面体A位与八面体B位离子间的超交换作用，进而提高铁氧体的居里温度。此外，微量MnCO₃的加入能增加晶格常数，提高初始磁导率和Q值。因此，通过多种微量掺杂剂的协同作用实现了对NiCuZn铁氧体材料性能的进一步优化，最终获得了综合性能优异的高磁导率高居里温度NiCuZn软磁铁氧体材料，满足了小型化、宽温度、高功率感性器件对软磁材料的要求。The overall train of thought of the present invention is as follows: the main component that the present invention adopts comprises Fe ₂ O ₃ , NiO, ZnO and CuO, these several main components have determined the main technical parameter (as initial magnetic permeability, Curie temperature, saturation flux density). In addition, the present invention uses Y ₂ O ₃ , MoO ₃ , V ₂ O ₅ , and MnCO ₃ trace element co-doping technology for the first time to maximize the beneficial effects of each trace element and the synergistic effect between ions. Proper amount of V ₂ O ₅ doping can make ferrite form a liquid phase for sintering and increase the magnetic permeability. The formation of a liquid phase during the sintering process helps trace elements such as Y ₂ O ₃ , MoO ₃ , MnCO ₃ to enter the grain boundary and play a role. The doping of a small amount of MoO ₃ can increase the ferrite grain size, improve the uniformity, and increase the initial magnetic permeability, but it will also cause a small decrease in the Curie temperature. And Y ₂ O ₃ can affect the super-exchange between the ferrite tetrahedral A-site and octahedral B-site ions, thereby increasing the Curie temperature of ferrite. In addition, the addition of a trace amount of MnCO ₃ can increase the lattice constant, improve the initial magnetic permeability and Q value. Therefore, through the synergistic effect of various trace dopants, the performance of NiCuZn ferrite material is further optimized, and finally a NiCuZn soft ferrite material with high magnetic permeability and high Curie temperature with excellent comprehensive performance is obtained, which meets the miniaturization requirements. , wide temperature, high power inductive devices require soft magnetic materials.

本发明所使用的原料均为工业级原料，价格低廉、产量较大、无毒无害，且制备过程简单、节能高效，便于产业化推广。The raw materials used in the present invention are all industrial-grade raw materials with low price, large output, non-toxic and harmless, simple preparation process, energy saving and high efficiency, and are convenient for industrialization promotion.

具体的，本发明高磁导率高居里温度NiCuZn软磁铁氧体材料的原料包含主成分和掺杂成分，以质量百分数计，主成分主要包含：Fe₂O₃:66.22wt％～68.65wt％；ZnO:18.30wt％～22.15wt％；NiO:7.75wt％～9.85wt％；余量为CuO。Specifically, the raw material of the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature in the present invention includes main components and doping components. In terms of mass percentage, the main components mainly include: Fe ₂ O ₃ : 66.22wt%-68.65wt% ; ZnO: 18.30wt% to 22.15wt%; NiO: 7.75wt% to 9.85wt%; the balance is CuO.

所述掺杂成分包含Y₂O₃、MoO₃、V₂O₅和MnCO₃，其中，Y₂O₃含量为主成分质量的0.05wt％～0.10wt％，MoO₃含量为主成分质量的0.06wt％～0.18wt％，V₂O₅含量为主成分质量的0.05wt％～0.15wt％，MnCO₃含量为主成分质量的0.04wt％～0.12wt％。掺杂成分的含量不超过主成分质量的0.55wt％。The doping components include Y ₂ O ₃ , MoO ₃ , V ₂ O ₅ and MnCO ₃ , wherein the Y ₂ O ₃ content is 0.05wt% to 0.10wt% of the main component mass, and the MoO ₃ content is 0.05 wt% of the main component mass 0.06wt% to 0.18wt%, the V ₂ O ₅ content is 0.05wt% to 0.15wt% of the main component mass, and the MnCO ₃ content is 0.04wt% to 0.12wt% of the main component mass. The content of the doping component is not more than 0.55wt% of the mass of the main component.

本发明高磁导率高居里温度NiCuZn软磁铁氧体材料的制备方法包括以下步骤：The preparation method of NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature of the present invention comprises the following steps:

(1)原材料混合：取纯度分别为Fe₂O₃≥99.40％、NiO≥99.20％、ZnO≥99.70％、CuO≥99.00％的粉末装入滚筒球磨机中，并装入耐磨钢球和超纯水，球磨罐中钢球：超纯水：粉料的重量比为5：(1.5±0.2)：1，转速100-120转/min，球磨3h～6h，结束后加入4wt％-6wt％的PVA胶水继续湿磨20-40min，得到混合料A。(1) Mixing of raw materials: Take powders with a purity of Fe ₂ O ₃ ≥99.40%, NiO ≥99.20%, ZnO ≥99.70%, CuO ≥99.00%, and put them into a roller mill, and put wear-resistant steel balls and ultra-pure Water, steel balls in the ball milling tank: ultrapure water: powder weight ratio is 5: (1.5±0.2): 1, rotating speed 100-120 rpm, ball milling 3h-6h, after the end, add 4wt%-6wt% The PVA glue continued to be wet-milled for 20-40min to obtain the mixture A.

(2)红喷造粒：将混合料A进行红喷造粒，喷雾塔出口温度为85℃-95℃，进口温度为170±10℃，所得物料的粒径为150±30μm；(2) Red spray granulation: carry out red spray granulation on the mixture A, the outlet temperature of the spray tower is 85°C-95°C, the inlet temperature is 170±10°C, and the particle size of the obtained material is 150±30 μm;

(3)高温预烧：将上述步骤(2)得到的红喷造粒料进行预烧，预烧温度为930℃～970℃，保温2.5±0.5h，保温结束自然冷却降温；(3) High-temperature pre-burning: pre-burn the red-spray granulated material obtained in the above step (2), the pre-burning temperature is 930°C to 970°C, keep the heat for 2.5±0.5h, and cool down naturally after the heat preservation;

(4)微量元素掺杂：将上述步骤(3)获得的预烧料进行破碎处理，所得破碎料的粒径范围为330±50μm，之后加入掺杂成分Y₂O₃:0.05wt％～0.10wt％；MoO₃:0.06wt％～0.18wt％；V₂O₅:0.05wt％～0.15wt％；MnCO₃:0.04wt％～0.12wt％。(4) Trace element doping: crush the calcined material obtained in the above step (3), the particle size range of the obtained crushed material is 330±50 μm, and then add the doping component Y ₂ O ₃ : 0.05wt%～0.10 wt%; MoO ₃ : 0.06wt%-0.18wt%; V ₂ O ₅ : 0.05wt%-0.15wt%; MnCO ₃ : 0.04wt%-0.12wt%.

(5)行星球磨：将上述步骤(4)所得配料装入行星式球磨机进行球磨，按磨球∶超纯水∶料＝4∶(1.5±0.2)∶1的质量比混合，以400±20转/min的转速球磨5.5h～6.5h，再加入4wt％-6wt％PVA胶水继续球磨20-40min，得到混合料B；(5) Planetary ball mill: the ingredients obtained in the above step (4) are loaded into a planetary ball mill for ball milling, and are mixed according to the mass ratio of balls: ultrapure water: material = 4: (1.5 ± 0.2): 1, with 400 ± 20 Ball mill for 5.5h to 6.5h at the speed of rotation/min, then add 4wt%-6wt% PVA glue and continue ball milling for 20-40min to obtain the mixture B;

(6)黑喷造粒：将上述步骤(5)制得的混合料B进行黑喷造粒，喷雾塔出口温度为80℃-90℃，进口温度为180±10℃，所得物料的粒径为100±30μm；(6) Black spray granulation: The mixture B prepared in the above step (5) is subjected to black spray granulation, the outlet temperature of the spray tower is 80°C-90°C, the inlet temperature is 180±10°C, the particle size of the obtained material 100±30μm;

(7)冷压成型：将上述步骤(6)制得的粉料按料重的(0.12±0.02)wt％加入硬脂酸锌作为脱模剂，并采用双向加压方式冷压成型，成型压力10±0.2MPa，

(7) Cold press forming: the powder material obtained in the above step (6) is added with zinc stearate as a release agent according to (0.12 ± 0.02) wt% of the material weight, and cold press formed by two-way pressurization, forming Pressure 10±0.2MPa,

(8)高温梯度烧结：对步骤(7)所述样环毛坯置于烧结炉中1150±20℃下进行烧结并保温2.5±0.5h，升温梯度如下：室温至470℃±30℃时以1.5±0.2℃/min的速率升温，在470℃±30℃保温2±0.2h，470℃±30℃至900℃时以3±0.2℃/min的速率升温，后以2±0.2℃/min的速率升温至1150℃±20℃并保温2.5±0.5h，结束后自然冷却至室温出炉，得到所述高磁导率高居里温度NiCuZn软磁铁氧体材料。所述高磁导率高居里温度NiCuZn软磁铁氧体材料的密度为5.27±0.1g/cm³。(8) High-temperature gradient sintering: place the sample ring blank in step (7) in a sintering furnace at 1150±20°C for sintering and keep it warm for 2.5±0.5h. Heating at a rate of ±0.2°C/min, holding at 470°C±30°C for 2±0.2h, heating at a rate of 3±0.2°C/min from 470°C±30°C to 900°C, and then at a rate of 2±0.2°C/min Raise the temperature to 1150°C±20°C and keep it warm for 2.5±0.5h, then naturally cool to room temperature and leave the furnace to obtain the NiCuZn soft ferrite material with high magnetic permeability and high Curie temperature. The density of the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature is 5.27±0.1g/cm ³ .

实施例1：Example 1:

本实施例高磁导率高居里温度NiCuZn软磁铁氧体材料的制备方法包括以下步骤：The preparation method of NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature in this embodiment comprises the following steps:

(1)原材料混合：取纯度分别为Fe₂O₃≥99.40％、NiO≥99.20％、ZnO≥99.70％、CuO≥99.00％的原料粉末，按如下配比称重：Fe₂O₃:66.22wt％；ZnO:22.15wt％；NiO:7.75wt％；余量为CuO。装入滚筒球磨机中，并装入耐磨钢球和超纯水，球磨罐中钢球：超纯水：粉料的重量比为5：1.7：1，转速100转/min，球磨3h，球磨结束后加入6wt％的PVA胶水继续湿磨40min，得到混合料A。(1) Mixing of raw materials: take raw material powders with the purity of Fe ₂ O ₃ ≥99.40%, NiO ≥99.20%, ZnO ≥99.70%, CuO ≥99.00%, and weigh them according to the following ratio: Fe ₂ O ₃ : 66.22wt %; ZnO: 22.15wt%; NiO: 7.75wt%; the balance is CuO. Put it into the roller ball mill, and put it into wear-resistant steel balls and ultrapure water. The weight ratio of steel balls: ultrapure water: powder in the ball mill tank is 5:1.7:1, the speed is 100 rpm, ball milling 3h, ball milling After the end, add 6wt% PVA glue and continue wet grinding for 40 minutes to obtain the mixture A.

(2)红喷造粒：将混合料A进行红喷造粒，喷雾塔出口温度为90℃，进口温度为180℃，所得物料的粒径范围为150±30μm；(2) Red spray granulation: Red spray granulation is carried out on the mixture A, the outlet temperature of the spray tower is 90°C, the inlet temperature is 180°C, and the particle size range of the obtained material is 150±30μm;

(3)高温预烧：将上述步骤(2)得到的红喷造粒料进行预烧，预烧温度设置为930℃，保温2h，保温结束自然冷却降温；(3) High-temperature pre-burning: pre-burn the red spray granulated material obtained in the above step (2), set the pre-burning temperature to 930°C, keep it warm for 2 hours, and cool down naturally after the heat preservation is over;

(4)微量元素掺杂：将上述步骤(3)获得的预烧料进行破碎处理，所得破碎料的粒径范围为330±50μm，之后加入掺杂成分Y₂O₃:0.10wt％；MoO₃:0.06wt％；V₂O₅:0.15wt％；MnCO₃:0.06wt％，掺杂成分的各组分添加量均以主成分的含量进行计算。(4) Trace element doping: crushing the calcined material obtained in the above step (3), the particle size range of the obtained crushed material is 330±50 μm, and then adding the doping component Y ₂ O ₃ :0.10wt%; MoO ₃ : 0.06wt%; V ₂ O ₅ : 0.15wt%; MnCO ₃ : 0.06wt%, the addition amount of each component of the doping component is calculated based on the content of the main component.

(5)行星球磨：将上述步骤(4)所得掺杂破碎后的预烧粉装入行星式球磨机进行球磨，按磨球∶超纯水∶料＝4∶1.3∶1的质量比混合，以380转/min的转速球磨6h，球磨结束后再加入6wt％PVA胶水球磨20min，得到混合料B；(5) planetary ball mill: put the calcined powder after the doping and crushing of the above-mentioned step (4) gained into a planetary ball mill and carry out ball milling, press balls: ultrapure water: mix in the mass ratio of material=4:1.3:1, with Ball mill at a speed of 380 rpm for 6 hours, and then add 6wt% PVA glue for ball milling for 20 minutes after the ball milling to obtain the mixture B;

(6)黑喷造粒：将上述步骤(5)制得的混合料B进行黑喷造粒，喷雾塔出口温度为80℃，进口温度为170℃，所得物料的粒径为100±30μm；(6) Black spray granulation: the mixture B prepared in the above step (5) is subjected to black spray granulation, the outlet temperature of the spray tower is 80 ° C, the inlet temperature is 170 ° C, and the particle size of the obtained material is 100 ± 30 μm;

(7)冷压成型：将上述步骤(6)制得的粉料按料重的0.10wt％加入硬脂酸锌作为脱模剂，并采用双向加压方式冷压成型，成型压力9.8MPa，

(7) cold press molding: the powder material that above-mentioned step (6) makes is added zinc stearate as mold release agent according to 0.10wt% of material weight, and adopts two-way pressing mode cold press molding, molding pressure 9.8MPa,

(8)高温梯度烧结：对步骤(7)所述样环毛坯置于烧结炉中1170℃下进行烧结并保温3h，升温梯度如下：室温至440℃时以1.7℃/min的速率升温，在440℃保温2.2h，440℃至900℃时以3.2℃/min的速率升温，后以2.2℃/min的速率升温至1170℃并保温3h，结束后自然冷却至室温出炉，得到所述高磁导率高居里温度NiCuZn软磁铁氧体材料。所述高磁导率高居里温度NiCuZn软磁铁氧体材料的密度为5.17g/cm³。(8) High-temperature gradient sintering: place the sample ring blank described in step (7) in a sintering furnace for sintering at 1170° C. and keep it warm for 3 hours. The temperature gradient is as follows: from room temperature to 440° C. Keep warm at 440°C for 2.2 hours, raise the temperature at a rate of 3.2°C/min from 440°C to 900°C, and then raise the temperature at a rate of 2.2°C/min to 1170°C and keep it for 3 hours. After the end, naturally cool to room temperature and take out the furnace to obtain the high magnetic High conductivity Curie temperature NiCuZn soft ferrite material. The density of the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature is 5.17g/cm ³ .

实施例2：Example 2:

本实施例高磁导率高居里温度NiCuZn软磁铁氧体材料的制备方法包括以下步骤：The preparation method of NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature in this embodiment comprises the following steps:

(1)原材料混合：取纯度分别为Fe₂O₃≥99.40％、NiO≥99.20％、ZnO≥99.70％、CuO≥99.00％的粉末，按如下配比称重：Fe₂O₃:67.47wt％；ZnO:21.03wt％；NiO:9.24wt％；余量为CuO。装入滚筒球磨机中，并装入耐磨钢球和超纯水，球磨罐中钢球：超纯水：粉料的重量比为5：1.5：1，球磨机转速为115转/min，球磨5h，结束后加入5wt％的PVA胶水湿磨30min，得到混合料A。(1) Mixing of raw materials: Take powders with the purity of Fe ₂ O ₃ ≥99.40%, NiO ≥99.20%, ZnO ≥99.70%, CuO ≥99.00%, and weigh them according to the following ratio: Fe ₂ O ₃ : 67.47wt% ; ZnO: 21.03wt%; NiO: 9.24wt%; the balance is CuO. Put it into the roller ball mill, and put it into wear-resistant steel balls and ultrapure water. The weight ratio of steel balls: ultrapure water: powder in the ball mill tank is 5:1.5:1, the speed of the ball mill is 115 rpm, and the ball mill is 5h , after the end, add 5wt% PVA glue for wet milling for 30min to obtain the mixture A.

(2)红喷造粒：将混合料A进行红喷造粒，喷雾塔出口温度为95℃，进口温度为190℃，所得物料的粒径范围为150±30μm；(2) Red spray granulation: Red spray granulation is carried out on the mixture A, the outlet temperature of the spray tower is 95°C, the inlet temperature is 190°C, and the particle size range of the obtained material is 150±30μm;

(3)高温预烧：将上述步骤(2)得到的红喷造粒料进行预烧，预烧温度为950℃，保温3h，保温结束后随炉自然冷却降温；(3) High-temperature pre-burning: pre-burning the red-sprayed granulated material obtained in the above step (2), the pre-burning temperature is 950 ° C, kept for 3 hours, and naturally cooled with the furnace after the heat preservation is completed;

(4)微量元素掺杂：将上述步骤(3)获得的预烧料进行破碎处理，所得破碎料的粒径范围为330±50μm，之后加入如下掺杂成分：Y₂O₃:0.08wt％；MoO₃:0.12wt％；V₂O₅:0.1wt％；MnCO₃:0.04wt％，掺杂成分的各组分添加量均以主成分的含量进行计算。(4) Trace element doping: crush the calcined material obtained in the above step (3), the particle size range of the obtained crushed material is 330±50 μm, and then add the following doping components: Y ₂ O ₃ : 0.08wt% ; MoO ₃ : 0.12wt%; V ₂ O ₅ : 0.1wt%; MnCO ₃ : 0.04wt%, the addition amount of each component of the doping component is calculated based on the content of the main component.

(5)行星球磨：将上述步骤(4)所得配料装入行星式球磨机进行球磨，按磨球∶超纯水∶料＝4∶1.5∶1的质量比混合，以420转/min的转速球磨5.5h，再加入5wt％PVA胶水球磨30min，得到混合料B；(5) planetary ball mill: the ingredients obtained in the above steps (4) are loaded into a planetary ball mill for ball milling, and are mixed according to the mass ratio of balls: ultrapure water: material = 4: 1.5: 1, and ball milled at a speed of 420 rpm 5.5h, then add 5wt% PVA glue and ball mill for 30min to obtain mixture B;

(6)黑喷造粒：将上述步骤(5)制得的混合料B进行黑喷造粒，喷雾塔出口温度为85℃，进口温度为180℃，所得物料的粒径为100±30μm；(6) Black-spray granulation: the mixture B prepared in the above step (5) is subjected to black-spray granulation, the outlet temperature of the spray tower is 85° C., the inlet temperature is 180° C., and the particle diameter of the obtained material is 100 ± 30 μm;

(7)冷压成型：将上述步骤(6)制得的粉料按料重的0.14wt％加入硬脂酸锌作为脱模剂，并采用双向加压方式冷压成型，成型压力10.2MPa，

(7) cold press molding: the powder material that above-mentioned step (6) is made adds zinc stearate as release agent according to 0.14wt% of material weight, and adopts two-way pressing mode cold press molding, molding pressure 10.2MPa,

(8)高温梯度烧结：对步骤(7)所述样环毛坯置于烧结炉中1150℃下进行烧结并保温2.5h，升温梯度如下：室温至470℃时以1.5℃/min的速率升温，在470℃保温2h，470℃至900℃时以3℃/min的速率升温，后以2℃/min的速率升温至1150℃并保温2.5h，结束后自然冷却至室温出炉，得到所述高磁导率高居里温度NiCuZn软磁铁氧体材料。所述高磁导率高居里温度NiCuZn软磁铁氧体材料的密度为5.37g/cm³。(8) High-temperature gradient sintering: place the sample ring blank described in step (7) in a sintering furnace at 1150°C for sintering and keep it warm for 2.5 hours. Insulate at 470°C for 2 hours, raise the temperature at a rate of 3°C/min from 470°C to 900°C, then raise the temperature at a rate of 2°C/min to 1150°C and keep it for 2.5 hours, and then naturally cool to room temperature and take out the furnace to obtain the high temperature High permeability NiCuZn soft magnetic ferrite material with high Curie temperature. The density of the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature is 5.37g/cm ³ .

实施例3：Example 3:

本实施例高磁导率高居里温度NiCuZn软磁铁氧体材料的制备方法包括以下步骤：The preparation method of NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature in this embodiment comprises the following steps:

(1)原材料混合：取纯度分别为Fe₂O₃≥99.40％、NiO≥99.20％、ZnO≥99.70％、CuO≥99.00％的粉末，按如下配比称重：Fe₂O₃:68.65wt％；ZnO:18.30wt％；NiO:9.85wt％；余量为CuO。装入滚筒球磨机中，并装入耐磨钢球和超纯水，球磨罐中钢球：超纯水：粉料的重量比为5：1.3：1，转速120转/min，球磨6h，结束后加入4wt％的PVA胶水湿磨20min，得到混合料A。(1) Mixing of raw materials: Take powders with the purity of Fe ₂ O ₃ ≥99.40%, NiO ≥99.20%, ZnO ≥99.70%, CuO ≥99.00%, and weigh them according to the following ratio: Fe ₂ O ₃ : 68.65wt% ; ZnO: 18.30wt%; NiO: 9.85wt%; the balance is CuO. Put it into the roller ball mill, and put it into wear-resistant steel balls and ultrapure water. The weight ratio of steel balls: ultrapure water: powder in the ball mill tank is 5:1.3:1, the speed is 120 rpm, ball milling 6h, end Then add 4wt% PVA glue and wet grind for 20min to obtain the mixture A.

(2)红喷造粒：将混合料A进行红喷造粒，喷雾塔出口温度为85℃，进口温度为170℃，所得物料的粒径为150±30μm；(2) Red spray granulation: Red spray granulation is carried out on the mixture A, the outlet temperature of the spray tower is 85 °C, the inlet temperature is 170 °C, and the particle size of the obtained material is 150 ± 30 μm;

(3)高温预烧：将上述步骤(2)得到的红喷造粒料进行预烧，预烧温度为970℃，保温2.5h，保温结束自然冷却降温；(3) High-temperature pre-burning: pre-burning the red-sprayed granulated material obtained in the above step (2), the pre-burning temperature is 970 ° C, kept for 2.5 hours, and cooled naturally after the heat preservation;

(4)微量元素掺杂：将上述步骤(3)获得的预烧料进行破碎处理，所得破碎料的粒径范围为330±50μm，之后加入掺杂成分Y₂O₃:0.05wt％；MoO₃:0.18wt％；V₂O₅:0.05wt％；MnCO₃:0.12wt％，掺杂成分的各组分添加量均以主成分的含量进行计算。(4) Trace element doping: crushing the calcined material obtained in the above step (3), the particle size range of the obtained crushed material is 330±50 μm, and then adding the doping component Y ₂ O ₃ :0.05wt%; MoO ₃ : 0.18wt%; V ₂ O ₅ : 0.05wt%; MnCO ₃ : 0.12wt%, the addition amount of each component of the doping component is calculated based on the content of the main component.

(5)行星球磨：将上述步骤(4)所得配料装入行星式球磨机进行球磨，按磨球∶超纯水∶料＝4∶1.7∶1的质量比混合，以400转/min的转速球磨6.5h，再加入4wt％PVA胶水球磨40min，得到混合料B；(5) planetary ball mill: the ingredients obtained in the above steps (4) are loaded into a planetary ball mill for ball milling, and are mixed according to the mass ratio of balls: ultrapure water: material = 4: 1.7: 1, and ball milled at a speed of 400 rpm 6.5h, then add 4wt% PVA glue and ball mill for 40min to obtain mixture B;

(6)黑喷造粒：将上述步骤(5)制得的混合料B进行黑喷造粒，喷雾塔出口温度为90℃，进口温度为190℃，所得物料的粒径为100±30μm；(6) Black spray granulation: the mixture B obtained in the above step (5) is subjected to black spray granulation, the outlet temperature of the spray tower is 90° C., the inlet temperature is 190° C., and the particle size of the obtained material is 100 ± 30 μm;

(7)冷压成型：将上述步骤(6)制得的粉料按料重的0.12wt％加入硬脂酸锌作为脱模剂，并采用双向加压方式冷压成型，成型压力10MPa，

(7) cold press molding: the powder material that above-mentioned step (6) is made adds zinc stearate as release agent according to 0.12wt% of material weight, and adopts two-way pressure mode cold press molding, molding pressure 10MPa,

(8)高温梯度烧结：对步骤(7)所述样环毛坯置于烧结炉中1130℃下进行烧结并保温2h，升温梯度如下：室温至500℃时以1.3℃/min的速率升温，在500℃保温1.8h，500℃至900℃时以2.8℃/min的速率升温，后以1.8℃/min的速率升温至1130℃并保温2h，结束后自然冷却至室温出炉，得到所述高磁导率高居里温度NiCuZn软磁铁氧体材料。所述高磁导率高居里温度NiCuZn软磁铁氧体材料的密度为5.25g/cm³。(8) High-temperature gradient sintering: place the sample ring blank described in step (7) in a sintering furnace for sintering at 1130° C. and keep it warm for 2 hours. The temperature gradient is as follows: from room temperature to 500° C. Incubate at 500°C for 1.8 hours, heat up at a rate of 2.8°C/min from 500°C to 900°C, then raise the temperature at a rate of 1.8°C/min to 1130°C and hold for 2 hours, then cool naturally to room temperature and take out the furnace to obtain the high magnetic High conductivity Curie temperature NiCuZn soft ferrite material. The density of the NiCuZn soft magnetic ferrite material with high magnetic permeability and high Curie temperature is 5.25g/cm ³ .

参见图1-图3，各实施例所制备样品性能测试结果如表1所示：Referring to Fig. 1-Fig. 3, the performance test results of the samples prepared in each embodiment are shown in Table 1:

表1Table 1

从表1可以看出，实施例2获得样品综合性能相对较优，100kHz测试频率下，初始磁导率μ_i为1665～2320，比损耗系数为28.78×10^-6，居里温度T_c＝145℃，饱和磁通密度B_s＝352mT(10kHz，4000A/m)，矫顽力H_c＝28.41A/m。此外，其还具有工作频率高、温度系数小等特点。此外，从上述实施例观察到实施例1样品具有相对最高的μ_i(2320)和最小的比损耗系数(13.24×10^-6)。It can be seen from Table 1 that the overall performance of the sample obtained in Example 2 is relatively good. At a test frequency of 100 kHz, the initial magnetic permeability μ _i is 1665-2320, the specific loss coefficient is 28.78×10 ^-6 , and the Curie temperature T _c = 145°C, saturation magnetic flux density B _s =352mT (10kHz, 4000A/m), coercive force H _c =28.41A/m. In addition, it also has the characteristics of high operating frequency and small temperature coefficient. In addition, it is observed from the above examples that the sample of Example 1 has the relatively highest μ _i (2320) and the smallest specific loss coefficient (13.24×10 ^-6 ).

以上所述，仅为本发明的优选实施例，应当指出，在不脱离本发明的核心技术前提下，还可以做出改进和变通，这些改进和变通也应属于本发明的专利保护范围。与本发明的权利要求书相当的含义和范围内的任何改变，都应认为是包括在权利要求书的范围内。The above is only a preferred embodiment of the present invention. It should be pointed out that without departing from the core technology of the present invention, improvements and modifications can also be made, and these improvements and modifications should also belong to the scope of patent protection of the present invention. Any changes within the meaning and scope equivalent to the claims of the present invention should be considered to be included in the scope of the claims.