WO2020140506A1 - 具有高工作频段的二维磁矩软磁复合材料及其制备方法 - Google Patents

具有高工作频段的二维磁矩软磁复合材料及其制备方法 Download PDF

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WO2020140506A1
WO2020140506A1 PCT/CN2019/108896 CN2019108896W WO2020140506A1 WO 2020140506 A1 WO2020140506 A1 WO 2020140506A1 CN 2019108896 W CN2019108896 W CN 2019108896W WO 2020140506 A1 WO2020140506 A1 WO 2020140506A1
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magnetic moment
dimensional
dimensional magnetic
fine powder
composite material
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French (fr)
Chinese (zh)
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汪小明
杨正
李发伸
郭春生
乔亮
王涛
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Lanzhou University
Guangzhou Newlife Magnet Electricity Co Ltd
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Lanzhou University
Guangzhou Newlife Magnet Electricity Co Ltd
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Definitions

  • the present invention generally relates to the field of magnetic materials, and more particularly, to a two-dimensional magnetic moment soft magnetic composite material, which has a higher operating frequency, thereby obtaining excellent high frequency and microwave frequency magnetic properties.
  • Laminated silicon steel sheet and soft ferrite are two types of traditional soft magnetic core materials. Among them, silicon steel sheet has high saturation magnetic induction strength, but as frequency increases, eddy current loss increases sharply, so it can only work at lower frequency. Generally below 1KHz.
  • the ferrite core has good high-frequency magnetic performance, the operating frequency can reach about 10MHz, and the resistivity is large, the eddy current loss is low, but there is a disadvantage of low magnetic flux density, so the conversion efficiency is not high. Both of these traditional soft magnetic materials encountered difficulties in the miniaturization of AC equipment.
  • soft magnetic composite materials which include fine powders of soft magnetic materials (generally Fe, FeSiAl, dispersed in organic or inorganic insulating material matrix) FeNi, etc.).
  • the soft magnetic composite material has a higher operating frequency than the laminated silicon steel sheet, for example, it can reach about 100KHz, and at the same time has a higher saturation magnetic induction intensity than the soft ferrite, so it has been widely used in some fields.
  • ⁇ i is the initial permeability
  • fr is the natural resonance frequency (or cut-off frequency)
  • ⁇ ' is the gyromagnetic ratio
  • Ms is the saturation magnetic induction intensity. Due to the limitation of the Snoek limit, the current working frequency of soft magnetic composite materials can only be below 100KHz-200KHz, which hinders the application of soft magnetic composite materials in the field of high-frequency microwaves.
  • One aspect of the present invention is to provide a two-dimensional magnetic moment soft magnetic composite material and a preparation method thereof.
  • the two-dimensional magnetic moment soft magnetic composite material can break through the Snoek limit, and thus can be applied to higher frequency bands, and contribute to the realization of Device miniaturization, light weight and energy saving.
  • a two-dimensional magnetic moment soft magnetic composite material including: an insulating matrix; and two-dimensional magnetic moment fine powder dispersed in the insulating matrix, wherein, inside the two-dimensional magnetic moment fine powder, magnetic Moments are distributed in a specific two-dimensional plane.
  • the two-dimensional magnetic moment fine powder includes at least one of artificial two-dimensional magnetic moment fine powder and intrinsic two-dimensional magnetic moment fine powder.
  • the artificial two-dimensional magnetic moment fine powder has a cubic crystal structure; the intrinsic two-dimensional magnetic moment fine powder has a non-cubic crystal structure, and the easy magnetization axis is perpendicular to the C axis.
  • the size of the artificial two-dimensional magnetic moment micropowder is below 20 ⁇ m, preferably below 15 ⁇ m, the thickness is below 500 nm, preferably below 100 nm, and the diameter-to-thickness ratio is in the range of 40 to 200, preferably at 50 To the range of 150.
  • the size of the intrinsic two-dimensional magnetic moment fine powder is below 10 ⁇ m, preferably below 5 ⁇ m.
  • the artificial two-dimensional magnetic moment micropowder includes one or more of the following materials: Fe, iron carbonyl, an alloy formed of at least one of Fe and Co, and Ni, FeSiAl, and FeNiMo.
  • the intrinsic two-dimensional magnetic moment micropowder includes one or more of the following materials: R 2 (Fe, Ni, Si, Al) 17 N 3 , where R is Y, Ce, Nd, or Pr ; Sm 2 (Fe, Ni, Co) 14 B; R 2 (Co, Fe, Ni) 17 , where R is Y or Nd.
  • the insulating matrix includes at least one of thermoplastic resin, thermosetting resin, and synthetic rubber.
  • the two-dimensional magnetic moment fine powder is oriented in the insulating matrix such that the magnetic moment of the two-dimensional magnetic moment fine powder is distributed in a two-dimensional plane.
  • an electronic device including: a circuit; and an insulating magnetic member disposed in the immediate vicinity of the circuit, the insulating magnetic member being made of the above two-dimensional magnetic moment soft magnetic composite material.
  • the electronic device is one of an inductor, an antenna, a microwave isolator, a microwave circulator, a phase shifter, a filter, and a transformer.
  • a method for preparing a two-dimensional magnetic moment soft magnetic composite material includes: preparing a two-dimensional magnetic moment fine powder, inside the two-dimensional magnetic moment fine powder, the magnetic moment is distributed in a specific two-dimensional plane; Uniformly dispersing the two-dimensional magnetic moment fine powder in an insulating matrix; and curing the insulating matrix.
  • the method further includes using an external magnetic field to orient the magnetic moment of the two-dimensional magnetic moment fine powder in the insulating matrix in a two-dimensional plane generated by the external magnetic field before curing the insulating matrix.
  • the two-dimensional magnetic moment soft magnetic composite material of the present invention can break through the Snoek limit of the traditional soft magnetic composite material, and still has good magnetic properties in high-frequency and microwave frequency bands, and is suitable for mass production, so it has wide application prospects.
  • FIG. 1 shows the distribution of magnetic moments in the intrinsic two-dimensional magnetic moment micropowder unit cell (left) and the distribution of magnetic moments in the artificial two-dimensional magnetic moment micropowder (right) according to an embodiment of the present invention.
  • FIG. 2 shows a schematic view of the spatial orientation of the internal magnetic moment of the two-dimensional magnetic moment composite material before (left) and after the external magnetic field orientation (right) according to an embodiment of the present invention.
  • Figure 3 shows the relationship between the demagnetization factor and the diameter-thickness ratio.
  • FIG. 4 shows a flowchart of a method for preparing a two-dimensional magnetic moment soft magnetic composite material according to an embodiment of the present invention.
  • FIG. 5 shows a Fe 57 Mossbauer spectrum of a two-dimensional magnetic moment soft magnetic composite material prepared according to an embodiment of the present invention.
  • Fig. 6 is a measurement result of hysteresis loops of the two-dimensional magnetic moment soft magnetic composite material of Fig. 5.
  • 7A and 7B are the magnetic spectra of the two-dimensional magnetic moment soft magnetic composite material of FIG. 5 in different frequency bands.
  • FIG. 8 shows XRD spectra of a two-dimensional magnetic moment soft magnetic composite material before and after orientation of an external magnetic field according to an embodiment of the present invention.
  • FIG. 1 shows the distribution of magnetic moments in the unit cell of intrinsic two-dimensional magnetic moment micropowder (left) and the distribution of magnetic moments in the artificial two-dimensional magnetic moment micropowder (right) according to an embodiment of the invention
  • FIG. 2 shows the distribution of magnetic moments in micropowder of artificial two-dimensional magnetic moment (right)
  • the two-dimensional magnetic moment soft magnetic composite material 100 may include an insulating matrix 110 and two-dimensional magnetic moment fine powder 120 dispersed in the insulating matrix 110.
  • the insulating matrix 110 may be those used in conventional soft magnetic composite materials, generally organic insulating materials, for example, organic polymer adhesives such as thermoplastic resins, thermosetting resins, and synthetic rubbers, examples of which may include but Not limited to polyurethane, polyimide, etc.
  • organic polymer adhesives such as thermoplastic resins, thermosetting resins, and synthetic rubbers, examples of which may include but Not limited to polyurethane, polyimide, etc.
  • the two-dimensional magnetic moment fine powder 120 is dispersed and fixed in the insulating matrix 110, so that the two-dimensional magnetic moment soft magnetic composite material 100 is an electrically insulating magnetic material.
  • the magnetic moment of the two-dimensional magnetic moment fine powder 120 is confined to a specific two-dimensional plane in the magnetic powder by its internal role, so it is called two-dimensional magnetic moment soft Magnetic composite material.
  • the two-dimensional magnetic moment soft magnetic composite material itself may have various physical shapes, such as a thin film shape, a three-dimensional block shape such as a cube and a rectangular block, and the like.
  • the magnetic moment of the two-dimensional magnetic moment fine powder 120 lies in a specific two-dimensional plane in the magnetic powder.
  • the two-dimensional magnetic moment micropowder 120 may include at least one of two types of micropowders, namely artificial two-dimensional magnetic moment micropowder and intrinsic two-dimensional magnetic moment micropowder, as shown in the right figure in FIG. 1, respectively. And shown on the left.
  • artificial two-dimensional magnetic moment micropowder is a material with intrinsic two-dimensional magnetic moment distribution
  • artificial two-dimensional magnetic moment micropowder is a material with artificial two-dimensional magnetic moment distribution, which will be described in detail below.
  • the intrinsic two-dimensional magnetic moment fine powder may include fine powder of a soft magnetic material having a non-cubic crystal structure, and all easy magnetization axes of the soft magnetic material (abbreviated as "easy axis") are perpendicular to the C axis of the crystal structure.
  • easy axis all easy magnetization axes of the soft magnetic material
  • non-cubic crystal structure magnetic materials such as some non-cubic crystal structure rare earth-3d transition metal compounds and some non-cubic crystal structure ferromagnetic alloys, it has strong magnetocrystalline anisotropy, and its magnetocrystalline anisotropy
  • the constant K 1 has a large absolute value but a negative value.
  • the easy axis is perpendicular to the C axis, and the magnetic moments are oriented along specific crystal planes such as the hexagonal plane and the C plane, thus forming a two-dimensional magnetic moment distribution.
  • the radial (or in-plane) anisotropy field H xy and normal (or out-of-plane) anisotropy field H z of this material are derived from the magnetocrystalline anisotropy of the material itself, so it is called intrinsic two Dimensional magnetic moment powder.
  • intrinsic two-dimensional magnetic moment micropowders include: R 2 (Fe, Ni, Si, Al) 17 N 3 , where R is Y, Ce, Nd, or Pr; Sm 2 (Fe, Ni, Co) 14 B; R 2 (Co, Ni, Fe) 17 , where R is Y or Nd, and so on.
  • the shape of the intrinsic two-dimensional magnetic moment fine powder is not particularly limited, and may be, for example, substantially spherical particles or flakes. No matter what shape, the magnetic moment is distributed along a specific crystal plane, such as a hexagonal plane, a C plane, etc. Form a two-dimensional magnetic moment structure.
  • the size of the intrinsic two-dimensional magnetic moment micropowder may be below 10 ⁇ m, preferably below 5 ⁇ m. It should be understood that when referring to the size of the micropowder herein, unless the context indicates otherwise, it generally refers to the size in the maximum length direction of the micropowder.
  • the artificial two-dimensional magnetic moment fine powder may include metal and alloy soft magnetic materials having a cubic crystal structure.
  • the magnetocrystalline anisotropy field is very small.
  • Figure 3 shows the relationship between the demagnetization factor and the diameter-thickness ratio. As shown in Fig. 3, as the diameter-thickness ratio increases, the normal (out-of-plane) demagnetization factor N out continues to increase and finally approaches 1, while the in-plane demagnetization factor N in continues to decrease and finally approaches 0. .
  • the magnetic moments in the powder are distributed in its XY plane Inside, a two-dimensional magnetic moment structure is formed.
  • the out-of-plane (or normal) anisotropic field H z comes from the demagnetizing field
  • the in-plane (or radial) anisotropic field H xy comes from the magnetocrystalline anisotropic field of the material itself. Because it has a two-dimensional magnetic moment structure by artificial processing into a specific shape, this type of material is also called artificial two-dimensional magnetic moment powder.
  • the artificial two-dimensional magnetic moment fine powder include: Fe, iron carbonyl, an alloy formed of at least one of Fe and Co, and Ni, FeSiAl, and FeNiMo.
  • the diameter ratio of the artificial two-dimensional magnetic moment fine powder may range from 40 to 200, preferably from 50 to 150. As mentioned above, the larger the diameter-thickness ratio, the more favorable it is to form a two-dimensional magnetic moment structure. Therefore, when the diameter-thickness ratio is greater than 50, it is preferable to realize a substantially good two-dimensional magnetic moment structure.
  • the diameter-to-thickness ratio may be below 200, preferably below 150, and more preferably below 100 .
  • the size of the artificial two-dimensional magnetic moment fine powder may be 20 ⁇ m or less, preferably 15 ⁇ m or less, and the thickness may be 500 nm or less, preferably 300 nm or less.
  • ⁇ i is the initial permeability
  • fr is the natural resonance frequency
  • ⁇ ' is the gyromagnetic ratio
  • Ms is the saturation magnetic induction
  • H z is the out-of-plane anisotropy field
  • H xy is the in-plane anisotropy field .
  • the out-of-plane anisotropy field H z is much larger than the in-plane anisotropy field H xy , which is generally three orders of magnitude larger, so when the external magnetic field is zero, the magnetic moment of the two-dimensional magnetic moment powder is distributed at In a specific plane; when the external magnetic field is not zero, the magnetic moment rotates or precesses along the plane under the action of the external magnetic field.
  • all magnetic powders can be oriented by applying a rotating magnetic field or a multi-polar magnetic field, so that the two-dimensional magnetic moments of all magnetic powders are oriented in a two-dimensional plane, thereby
  • the permeability of the two-dimensional magnetic moment soft magnetic composite material in the orientation field of the external field is much higher than that of the non-oriented material, which can theoretically be increased by 1.5 times, and it is isotropic in the orientation plane.
  • the method 200 may start in step S210 to prepare a two-dimensional magnetic moment fine powder 120.
  • the preparation steps of the micropowder are relatively simple.
  • conventional methods such as quick-setting method, smelting ingot crushing method, reduction diffusion method, etc. can be used to prepare the initial powder, or the initial powder can be purchased directly and then processed with a high-energy ball mill or sand mill to refine the magnetic powder to 10 ⁇ m Below, preferably 5 ⁇ m or less.
  • the size is less than 5-20 ⁇ m, or the magnetic powder can be purchased directly.
  • the magnetic powder is treated with a high-energy ball mill or a sand mill, and the grinding process is optimized so that the diameter-thickness ratio of most of the fine powders obtained is more than 40, preferably more than 50, and the thickness is less than 500 nm, preferably less than 300 nm. It should be understood that adjusting the diameter-to-thickness ratio by optimizing the ball milling process is known to those skilled in the related art and will not be repeated here.
  • the prepared two-dimensional magnetic moment fine powder 120 may be uniformly dispersed in an insulating matrix 110 such as a polymer binder, which may be achieved by, for example, mixing and stirring steps.
  • step S230 all the two-dimensional magnetic moment fine powder 120 in the insulating matrix 110 can be oriented using an externally oriented magnetic field.
  • the two-dimensional magnetic moment fine powder 120 can be oriented in the plane generated by the external field by a rotating magnetic field, a multi-pole magnetic field, or the like. It should be understood that in step S230, since the two-dimensional magnetic moment micropowder 120 can slowly rotate in the organic insulating matrix 110 with appropriate viscosity, through the orientation step S230, the easy magnetization plane of all micropowders 120 can be oriented in the external field. Dimension plane.
  • the insulating matrix can be cured to obtain a certain shape, and the two-dimensional magnetic moment soft magnetic fine powder 120 is fixed in the insulating matrix 110.
  • corresponding curing means may be used, such as heating, ultraviolet irradiation, pressurization, natural curing, and the like.
  • step S240 may be directly performed without going through the orientation step S230, and a desired shape such as a block, a column, a film, etc. may be prepared by processes such as calendering, molding, extrusion, injection, or casting. 2D magnetic moment soft magnetic composite material.
  • a desired shape such as a block, a column, a film, etc.
  • processes such as calendering, molding, extrusion, injection, or casting.
  • 2D magnetic moment soft magnetic composite material may be directly performed without going through the orientation step S230, and a desired shape such as a block, a column, a film, etc.
  • performing step S230 is preferable because the magnetic permeability of the two-dimensional magnetic moment soft magnetic composite material can be improved.
  • the "two-dimensional magnetic moment" of the present invention can be understood on two levels.
  • the magnetic moments are distributed in a two-dimensional plane, which can increase the natural resonance frequency of the material, thereby making the material available for higher frequency bands such as high frequencies and microwaves.
  • the magnetic moments of all the fine powders can be oriented in multiple two-dimensional planes parallel to each other, thereby increasing the magnetic permeability.
  • the second point is only preferable, not necessary.
  • the raw powder before the ball milling process is a commercially available carbonyl iron powder, the model is MCIP-4, and the size is 4 to 5 microns.
  • the high-energy ball mill or sand mill is used to grind the carbonyl iron powder to obtain two-dimensional magnetic moment fine powder with high diameter-to-thickness ratio.
  • the fine powder and polyurethane are uniformly mixed, the volume concentration of the magnetic powder is 65%, orientated in a rotating magnetic field (2T), compacted, and the unidirectional pressure is 3 MPa to obtain a sample.
  • Figure 5 is the Fe 57 Mossbauer spectrum of the sample. This data shows that the plane orientation of the magnetic moment of the composite material sample obtained by the present invention is better than 95%.
  • Figure 6 shows the results of hysteresis loop measurements in three directions of X, Y, and Z on a vibrating sample magnetometer (VSM), indicating that the sample is easier to magnetize and isotropic in the XY plane, and its magnetic moment The degree of plane orientation is better than 95%.
  • 7A and 7B are magnetic spectra of the two-dimensional magnetic moment soft magnetic composite material of FIG. 5 in different frequency bands, where the frequency band corresponding to FIG. 7A is 1-110 MHz, and the frequency band corresponding to FIG. 7B is 0.1-18 GHz.
  • Table 1 shows the real part ⁇ 'and imaginary part ⁇ 'and Q value of the permeability of several characteristic points in the 10-110MHz frequency band. It can be seen that the two-dimensional magnetic moment soft magnetic composite of Example 1 can It works well in the high frequency range of 1-100MHz, the corresponding real part of permeability is about 25-27, and the Q value is 181-9.
  • FeNi two-dimensional magnetic moment soft magnetic composite material The original powder before ball milling is commercially available iron-nickel powder with a size of 15-20 microns. Using a high-energy ball mill or sand mill, and using optimized ball mill conditions, two-dimensional magnetic moment fine powder with a diameter to thickness ratio of 30-50 is obtained. FeNi two-dimensional magnetic moment micropowder and polyurethane are uniformly mixed, the volume concentration of the magnetic powder is 30%, the pressure is knotted in a rotating magnetic field (2T), and the unidirectional pressure is 3 MPa to obtain a sample.
  • 2T rotating magnetic field
  • the sample was also subjected to Fe 57 Mössbauer spectrum measurement and vibration sample magnetometer measurement.
  • the measurement results (not shown) indicate that the sample is more easily magnetized in the XY plane and has isotropy, and the plane orientation of its magnetic moment Degree is better than 95%.
  • the magnetic spectra of the 1-110MHz and 0.1-18GHz bands were also measured on this sample.
  • Table 2 below shows the real part ⁇ 'and imaginary part ⁇ of the permeability of several characteristic points in the 1-110MHz band" and Q value. It can be seen that the 2D magnetic moment soft magnetic composite material of Example 2 can also work well in the high frequency range of 1-100MHz, the corresponding real part of the permeability is about 25, and the Q value is 283- 4.
  • NdFeN two-dimensional magnetic moment soft magnetic composite material Nd 2 Fe 17 spherical fine powder was prepared by reduction diffusion method, and after nitridation, Nd 2 Fe 17 N 3- ⁇ two - dimensional magnetic moment fine powder was obtained. Optimize the ball milling process to obtain two-dimensional magnetic moment fine powder with appropriate particle size.
  • the micropowder and polyurethane are uniformly mixed, the volume concentration of the magnetic powder is 65%, orientated in a rotating magnetic field or a multipolar magnetic field (2T), and compacted (unidirectional pressure 3MPa) to obtain a composite material sample.
  • the NdFeN two-dimensional magnetic moment soft magnetic composite material of Example 3 was subjected to XRD measurement before and after the orientation of the external magnetic field, and the measurement results are shown in FIG. 8. It can be seen from Fig. 8 that the (006) peak is significantly enhanced after the orientation, and the calculation shows that the orientation degree of the magnetic moment plane of the Nd 2 Fe 17 N 3- ⁇ two - dimensional magnetic moment soft magnetic composite is better than 95%.
  • the Mössbauer spectrum measurement is consistent with the measurement results of the vibrating sample magnetometer.
  • the magnetic spectra of the 1-110MHz and 0.1-18GHz bands were also measured on this sample. Table 3 below shows the magnetic permeability and Q values of several characteristic points in the 1MHz to 10GHz band.
  • the working frequency of the two-dimensional magnetic moment soft magnetic composite material of Example 3 can be as high as about 10 GHz, and the corresponding magnetic permeability is about 7.5-2. By optimizing the preparation process, there is still much room for improvement in its high-frequency permeability.
  • the two-dimensional magnetic moment soft magnetic composite material of the present invention can be applied to various devices, especially devices with high-frequency and microwave band operating frequencies. Therefore, some embodiments of the present invention also provide an electronic device that includes a circuit and an insulating magnetic component disposed next to the circuit.
  • the circuit may be a coil, a resonant circuit, etc.
  • the insulating magnetic component disposed next to the circuit may be a core, etc., which may be composed of a two-dimensional magnetic moment soft magnetic composite according to the above embodiments of the present invention Made of materials.
  • Examples of such electronic devices include, but are not limited to, inductors, antennas, microwave isolators, microwave circulators, phase shifters, filters, and transformers. Since the structures of these devices are known, the description will not be repeated here. In other embodiments of the present invention, electronic equipment including these electronic devices is also provided.

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