阅读说明：本技术 芯-壳颗粒、磁介电材料、其制造方法和用途 (Core-shell particles, magneto-dielectric materials, methods of manufacture and uses thereof ) 是由 陈亚杰 卡尔·爱德华·施普伦托尔 克里斯季·潘采 于 2019-01-09 设计创作，主要内容包括：在一个方面,磁性颗粒包括：芯,所述芯包含铁和包括钴、镍或其组合的第二金属,其中铁与第二金属的芯原子比为50:50至75:25；以及壳,所述壳至少部分地包围芯并且包含铁氧化物、铁氮化物或其组合和第二金属。在另一个方面,磁介电材料包含聚合物基体和多个磁性颗粒；其中磁介电材料在1GHz下的磁损耗角正切小于或等于0.07。(In one aspect, a magnetic particle comprises: a core comprising iron and a second metal comprising cobalt, nickel, or a combination thereof, wherein the core atomic ratio of iron to the second metal is from 50:50 to 75: 25; and a shell at least partially surrounding the core and comprising an iron oxide, an iron nitride, or a combination thereof, and a second metal. In another aspect, a magneto-dielectric material comprises a polymer matrix and a plurality of magnetic particles; wherein the magnetic loss tangent of the magneto-dielectric material at 1GHz is less than or equal to 0.07.)

1. A magnetic particle comprising:

a core, said core comprising

Iron, and

a second metal comprising cobalt, nickel, or a combination thereof,

wherein the core atomic ratio of the iron to the second metal is from 50:50 to 75: 25; and

a shell at least partially surrounding the core and comprising

Iron oxide, iron nitride or combinations thereof, and

the second metal.

2. The magnetic particle of claim 1 wherein the shell has at least one of:

a higher resistivity than the core, or

A permeability of greater than or equal to 1 or greater than or equal to 5, each determined at 1 GHz.

3. The magnetic particle according to any one or more of the preceding claims, wherein

At least one of the core and the shell further comprising Cr, Ba, Au, Ag, Cu, Gd, Pt, Bi, Ir, Mn, Mg, Mo, Nb, Nd, Sr, V, Zn, Zr, N, C, or a combination thereof,

preferably, wherein the core and the shell further comprise the same one or more of Cr, Ba, Au, Ag, Cu, Gd, Pt, Bi, Ir, Mn, Mg, Mo, Nb, Nd, Sr, V, Zn, Zr, N, C, or combinations thereof.

4. The magnetic particle of any one or more of the preceding claims, wherein the core atomic ratio of the iron to the second metal is from 60:40 to 70:30 or from 65:35 to 70: 30.

5. The magnetic particle of any one or more of the preceding claims, wherein the shell atomic ratio of iron in the shell to the second metal in the shell is from 50:50 to 75: 25.

6. The magnetic particle of any one or more of the preceding claims, wherein the shell comprises the iron nitride.

7. The magnetic particles of any one or more of the preceding claims, wherein the iron oxide comprises magnetite having formula M_xFe_yO_zOr a combination thereof; wherein M comprises at least one of Co, Ni, Zn, V, Mn, or combinations thereof.

8. The magnetic particle of any one or more of the preceding claims, wherein the shell comprises the iron oxide; wherein the iron oxide comprises the formula MFe₂O₄、MFe₁₂O₁₉、Fe₃O₄、MFe₂₄O₄₁Or a combination thereof; wherein M comprises nickel, cobalt, or a combination thereof.

9. The magnetic particles according to at least one of the preceding claims, wherein the magnetic particles comprise irregularly shaped particles, spherical particles, ellipsoidal particles, rod-shaped particles, flakes, fibers, or combinations thereof.

10. The magnetic particles of any one or more of the preceding claims, wherein a plurality of the magnetic particles have at least one of:

the core has an average shortest dimension of 10nm to 5mm, or 10nm to 1 micron, or 100nm to 600 nm; or

The average shell thickness is less than or equal to 1 micron, from 1nm to 500 microns, or from 5nm to 50nm or from 5nm to 10 nm.

11. A method of forming a magnetic particle as claimed in any one or more of claims 1 to 10 comprising oxidising a core with an oxidising agent to form a shell;

preferably, wherein the oxidant comprises oxygen, KMnO₃、H₂O₂、K₂Cr₂O₇、HNO₃Or a combination thereof.

12. A magneto-dielectric material comprising:

a polymer matrix;

a plurality of magnetic particles according to any one or more of the preceding claims;

wherein the magnetic loss tangent of the magneto-dielectric material at 1GHz is less than or equal to 0.07.

13. The magneto-dielectric material of claim 12, wherein the magneto-dielectric material comprises 5 to 60 volume percent of the plurality of magnetic particles based on the total volume of the magneto-dielectric material.

14. The magneto-dielectric material of any one or more of claims 12-13, wherein the magneto-dielectric material further comprises a dielectric filler, a flame retardant, or a combination thereof.

15. The magneto-dielectric material of any one or more of claims 12-14, in the form of a layer and further comprising a conductive layer disposed on a surface of the layer.

16. The magneto-dielectric material of any one or more of claims 12-15, wherein the polymer matrix comprises a polyolefin, polyurethane, polyethylene, silicone, polyether, poly (phenylene sulfide), polybutadiene, polyisoprene, norbornene polymer, or a combination thereof.

17. A method of manufacturing the magneto-dielectric material of any one or more of claims 12-16, wherein the polymer matrix comprises a thermoplastic polymer, the method comprising injection molding the polymer and the plurality of magnetic particles.

18. A method of making the magneto-dielectric material of any one or more of claims 12 to 16, wherein the polymer matrix comprises a thermosetting polymer, and the method comprises reaction injection molding the polymer precursor composition and the plurality of magnetic particles.

19. An article comprising the magneto-dielectric material of any one or more of claims 12 to 18.

20. The article of claim 19, wherein the article is an antenna, a transformer, an anti-electromagnetic interference material, or an inductor.

21. The article of claim 19, wherein the article is a microwave device.

22. The article of any one or more of claims 19 to 21, comprising the magneto-dielectric material and a dielectric material comprising 0 to 2 volume percent magnetic particles, based on the total volume of the dielectric material.

Background

The present disclosure relates generally to core-shell particles, magneto-dielectric materials, methods of making, and uses thereof.

Newer design and manufacturing techniques have driven the size of electronic components, such as inductors on electronic integrated circuit chips, electronic circuits, electronic packages, modules, housings, and antennas, for example, to become smaller. One approach to reducing the size of electronic components is to use magneto-dielectric materials as substrates. In particular, ferrite, ferroelectric, and multiferroic materials have been widely studied as functional materials having enhanced microwave characteristics. However, these materials are not entirely satisfactory in that they often do not provide the desired bandwidth, and they can exhibit high magnetic losses at high frequencies (e.g., in the gigahertz range).

Thus, there remains a need in the art for magneto-dielectric materials with low magnetic losses in the gigahertz range.

Disclosure of Invention

Disclosed herein are magnetic particles comprising: a core comprising iron and a second metal comprising cobalt, nickel, or a combination thereof, wherein the core atomic ratio of iron to the second metal is from 50:50 to 75: 25; and a shell at least partially surrounding the core and comprising an iron oxide, an iron nitride, or a combination thereof, and a second metal.

Making the above magnetic particlesThe method comprises the following steps: oxidizing the core with an oxidizing agent to form a shell; preferably, wherein the oxidant comprises oxygen, KMnO₃、H₂O₂、K₂Cr₂O₇、HNO₃Or a combination thereof.

Disclosed herein is a magneto-dielectric material comprising a polymer matrix and a plurality of magnetic particles, wherein the magneto-dielectric material has a magnetic loss tangent of less than or equal to 0.07 at 1 gigahertz (GHz).

One method of making the above magneto-dielectric material includes injection molding a polymer and a plurality of magnetic particles.

Another method of making the above magneto-dielectric material includes reaction injection molding the polymer precursor composition and the plurality of magnetic particles.

Also described are articles comprising the magneto-dielectric material and the composite material, including an antenna, a transformer, an anti-electromagnetic interference material, or an inductor.

The above described and other features are exemplified by the following figures, detailed description, and claims.

Drawings

The following figures are exemplary aspects in which like elements are numbered alike.

FIG. 1 is an illustration of one aspect of a cross-section of a core-shell particle;

FIG. 2 is a diagrammatic representation of one aspect of a magneto-dielectric material;

FIG. 3 is an illustration of an aspect of a conductive layer disposed on a magneto-dielectric material;

FIG. 4 is a diagrammatic view of one aspect of a patterned conductive layer disposed on a magneto-dielectric material;

FIG. 5 is a diagrammatic representation of one aspect of a dual frequency magneto-dielectric material;

FIG. 6 is a diagrammatic representation of one aspect of preparing a magneto-dielectric material;

FIG. 7 is a scanning electron micrograph of the magnetic particles of example 2;

FIG. 8 is a scanning electron micrograph of the magnetic particles of example 5;

FIG. 9 is a graphical illustration of permeability versus frequency for examples 2,5 and 6;

FIG. 10 is a scanning electron micrograph of the magnetic particles of example 7;

FIG. 11 is a scanning electron micrograph of the magnetic particles of example 8; and

FIG. 12 is a graphical illustration of permeability versus frequency for examples 7 and 8.

Detailed Description

At high frequencies (e.g., greater than or equal to 500 megahertz (MHz) or greater than or equal to 1GHz), the conduction current is generally concentrated near the surface of the conductor, with the current density decreasing with increasing depth into the conductor and away from the surface. Skin depth is often used to define this reduction in current density and is defined herein as a depth below the surface: at the surface, the current density is reduced from that at the conductor surface to a factor of e (about 2.78). In particular, skin depth_sCan be determined by the formula (1).

Where ρ is the volume resistivity in ohms-meters (Ohm-m) and f is the frequency in hertz, μ₀Is 4 π x10^-7Permeability constant of Henry/m, and mu_rIs the relative magnetic permeability. Equation (1) illustrates that for a given material having bulk resistivity and relative permeability, the skin depth decreases as the frequency increases. For magnetic materials, the skin depth is often further reduced due to the increase in relative permeability, making such materials unsuitable for use at high frequencies.

It has surprisingly been found that magnetic particles having an increased skin depth can be formed by providing an oxide shell around a magnetic core. Specifically, the core of the magnetic particle comprises iron and further comprises nickel, cobalt or a combination thereof; and the shell of the magnetic particle comprises iron oxide, iron nitride, or a combination thereof. The presence of a resistive shell allows to reduce the magnetic losses while maintaining at the same time a high permeability and a high resistivity. For example, the magnetic permeability of the shell at a frequency of 1GHz or at a frequency of 1GHz to 10GHz may be greater than or equal to 5. The resistivity of the shell canAt more than or equal to 10⁵Ohm-m. Without being bound by theory, it is believed that the skin depth of the shell may be greater than or equal to 5 millimeters (mm), and thus, the core-shell magnetic particles as a whole may have a skin depth in the millimeter range (e.g., greater than or equal to 5 mm). The skin depth of the core-shell magnetic particles may be reduced by the skin depth of the core, which may be only a few microns. The core-shell structure may therefore be advantageous in that particles of greater skin depth than the core material may be used. In particular, it can be difficult to incorporate ferromagnetic metal particles having a sub-skin depth size into a polymer composition, and this can be hazardous, e.g., flammable, making the composite more difficult to manufacture or hazardous to use.

When used in a magneto-dielectric material comprising a polymer matrix and a plurality of core-shell magnetic particles, it has further been found that the magneto-dielectric material can have a magnetic loss tangent of less than or equal to 0.07 at 1GHz or 1GHz to 10 GHz. Magneto-dielectric materials with such low magnetic losses may be advantageously used in high frequency applications (e.g., in antenna applications).

The magnetic particles have a core-shell structure. The core of the magnetic particle comprises iron and further comprises a second metal comprising nickel, cobalt, or a combination thereof. The core may further comprise Cr, Au, Ag, Cu, Gd, Pt, Ba, Bi, Ir, Mn, Mg, Mo, Nb, Nd, Sr, V, Zn, Zr, N, C, or combinations thereof. The core may contain Ba. The core may include 0.001 to 20 atomic percent or 0.001 to 5 atomic percent of a non-magnetic metal such as carbon and nitrogen.

The core may comprise iron and a second metal comprising one or both of nickel and cobalt, and the atomic ratio of iron to the second metal may be from 50:50 to 75:25, or from 60:40 to 70:30, or from 65:35 to 70: 30.

The shell of the magnetic particles at least partially surrounds the core. For example, the shell may cover from 5% to 100%, or from 10% to 80%, or from 10% to 50% of the total surface area of the core material. The shell of the magnetic particle comprises iron oxide, iron nitride, or a combination thereof and also comprises a second metal comprising cobalt, nickel, or a combination thereof. The shell may further comprise Cr, Ba, Au, Ag, Cu, Gd, Pt, Bi, Ir, Mn, Mg, Mo, Nb, Nd, Sr, Gd, and,V, Zn, Zr, N, C, or a combination thereof. In one aspect, if one or more of the foregoing substances are present in the core, they are also present in the shell. The shell may comprise iron nitride. The shell may comprise iron not in the form of iron oxide or iron nitride. The iron oxide may comprise magnetite (Fe)₃O₄). Iron oxides may include, for example, iron oxides having the formula M_xFe_yO_zThe metallic iron oxide of (1), wherein M comprises at least one of Co, Ni, Zn, V, Mn, or a combination thereof. Specifically, M may include Co, Ni, or a combination thereof. The metallic iron oxide may have the formula MFe₂O₄、MFe₁₂O₁₉、Fe₃O₄、MFe₂₄O₄₁Or a combination thereof. In particular, the metallic iron oxide may comprise the formula MFe₂O₄Wherein M comprises nickel, cobalt, or a combination thereof.

The shell may comprise an oxide of the same or different material as the core. In particular, the shell may comprise an oxide of the same material as the core. For example, the shell and the core may comprise iron and a second metal, wherein the ratio of iron to the second metal may be the same, e.g., the ratio of the core and the shell may be within 1% of each other.

The shell may isolate the core from environmental degradation. The shell may have a higher resistivity than the core. The shell can have a resistivity greater than or equal to 10 at a temperature of 23 degrees Celsius (C.)⁵Ohm-m。

The magnetic particles may comprise irregularly shaped particles, spherical particles, flakes, fibers, rod-shaped particles, acicular particles, or a combination thereof. The aspect ratio of the magnetic particles, meaning longest dimension to shortest dimension (e.g., fiber length to fiber diameter), can be greater than or equal to 1 or greater than or equal to 10. The magnetic particles may be solid or hollow.

The magnetic particles may include hollow particles in which the particles have a hollow space in the core. Although a description of the theory of operation need not be provided, and the appended claims should not be limited by statements regarding such theory, it is believed that the advantages of the hollow particles are: deeper than one to two skin depths within the magnetic particle, an additional path for eddy currents is created without increasing the permeability of the magneto-dielectric material, ultimately creating an electrical advantage. The hollow particles may be formed by: coating a metal (e.g., ferric chloride) on a template material (e.g., polystyrene particles); and the template material is removed, for example, by heating to a temperature above the degradation temperature of the template material. The hollow particles may alternatively be formed by a sol-gel process.

The average shortest dimension of the magnetic particles prior to oxidation may be less than or equal to 6mm, less than or equal to 5mm, or from 0.01 microns to 2mm, or from 0.01 microns to 0.9 microns, or from 0.05 microns to 0.9 microns. As used herein, average shortest dimension refers to the average of the shortest length dimension that can be determined for a desired dimension. For example, the average shortest dimension of a spherical particle refers to the average diameter of the spherical particle, and the average shortest dimension of a fiber refers to the average diameter of the cross section of the fiber. Fig. 1 is an illustration of a cross-section of a core-shell particle (e.g., a core-shell particle of a sphere or fiber) having a core 12 and a shell 14. The average shortest dimension of the core 12 of the core-shell particle is the diameter D and the shell thickness is the thickness t. The core-shell particle may comprise a discrete boundary between the core and the shell (e.g., as shown in fig. 1), or there may be a diffusion boundary between the core and the shell, wherein the concentration of iron oxide increases from a position on the diffusion boundary with increasing distance from the center of the particle until the concentration optionally levels off with further increasing distance from the center to the surface of the particle.

The relative thickness of the shell can be determined by referring to equation (1). Equation (1) illustrates that if the thickness of the shell is too thin, the shell will not provide the desired resistivity, and further, there is a possibility that the particles may agglomerate or increased quantum tunneling may occur. If the shell is too thick, e.g., greater than or equal to the skin depth of the core-shell magnetic particles, the core may not contribute to the composite permeability of the magnetic particles. Thus, the shell thickness is selected to be less than or equal to the skin depth, but thick enough to provide the desired resistivity.

In some aspects, and without being bound by theory, the relative thickness t of the shell may be determined by reference to equation (1), where the lower limit of the shell thickness is defined by quantum tunneling effects (which are not desirable effects as they may lead to significant sources of loss). As such, the shell should be thick enough to avoid quantum tunneling of electrons from adjacent core particles. For quantum tunneling lengths, a thickness of a few nanometers (nm) is a reasonable assumption. The quantum tunneling length of most metals is in the range of 1 to 4 nanometers, more typically 2 to 3 nanometers. For the upper limit, to avoid undesirable variations of the Electromagnetic (EM) field and its source within the skin depth, a reasonable upper limit for the shell thickness is a shell thickness that is less than about 0.25 times the skin depth (). For one aspect as disclosed herein, having a skin depth of about 22mm, a shell thickness of about 5mm is produced. Thus, the shell thickness may be 1nm to 5nm, or 2nm to 3nm, or 1mm to 22mm, or 1mm to 10mm, or 1mm to 5 mm. To provide core-shell particles having the desired characteristics disclosed herein, it is desirable that the shell thickness t is less than the average shortest dimension D of the core, and that D is less than 0.25 times the skin depth. Thus, a reasonable upper limit for the shell thickness t is t ≦ D ≦ 4, where the reasonable lower limit is defined by quantum tunneling effects, as described above. The average shortest dimension D of the cores of the plurality of magnetic particles may vary within the above-described ranges to provide suitable results.

The permeability of the shell at a frequency of 1GHz or 1GHz to 10GHz may be greater than or equal to 1 or greater than or equal to 5.

The magneto-dielectric material may comprise 5 to 60 volume percent (vol%), or 10 to 50 vol%, or 15 to 45 vol% magnetic particles based on the total volume of the magneto-dielectric material.

An illustration of one aspect of the magneto-dielectric material is shown in fig. 2 and 3. Fig. 2 shows that the magneto-dielectric material 10 comprises a polymer matrix 16 and a plurality of core-shell magnetic particles comprising a core 12 and a shell 14. Fig. 3 shows that the magneto-dielectric material may further comprise a conductive layer 20. Fig. 4 shows that the magneto-dielectric material may also include a patterned conductive layer 20.

The magneto-dielectric material may contain a dielectric filler. Dielectric fillers may include, for example, titanium dioxide (including rutile and anatase), barium titanate, strontium titanate, silicon dioxide (including fused amorphous silica)Silicon nitride), corundum, wollastonite, Ba₂Ti₉O₂₀Solid glass spheres, synthetic glass or ceramic hollow spheres, quartz, boron nitride, aluminum nitride, silicon carbide, beryllium oxide, aluminum oxide, alumina trihydrate, magnesium oxide, mica, talc, nanoclay, magnesium hydroxide, or combinations thereof.

The dielectric filler may be surface treated with a silicon-containing coating, for example, an organofunctional alkoxysilane coupling agent. Zirconate or titanate coupling agents may be used. Such coupling agents may improve the dispersion of the filler in the polymer matrix and reduce water absorption of the finished composite circuit substrate. The filler component may comprise 30 to 70 volume percent of fused amorphous silica as a second filler, based on the weight of the filler.

The magneto-dielectric material may comprise 5 to 60 volume percent, or 10 to 50 volume percent, or 15 to 45 volume percent of the dielectric filler, based on the total volume of the magneto-dielectric material.

The magneto-dielectric material may include a flame retardant. The flame retardant may be halogenated or non-halogenated. The flame retardant may be present in the magneto-dielectric material in an amount of 0 to 30 vol% based on the volume of the magneto-dielectric material.

The flame retardant may be inorganic and may be present in the form of particles. The inorganic flame retardant may include a metal hydrate having a volume average particle diameter of, for example, 1nm to 500nm, or 1nm to 200nm, or 5nm to 200nm, or 10nm to 200 nm; alternatively, the volume average particle size may be 500nm to 15 microns, for example, 1 micron to 5 microns. The metal hydrate may include a hydrate of a metal such as Mg, Ca, Al, Fe, Zn, Ba, Cu, Ni, or a combination thereof. Hydrates of Mg, Al or Ca may be used. Examples of the hydrate include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, iron hydroxide, zinc hydroxide, copper hydroxide, and nickel hydroxide; and hydrates of calcium aluminate, dihydrate gypsum, zinc borate, and barium metaborate. Complexes of these hydrates, such as hydrates comprising Mg and at least one of Ca, Al, Fe, Zn, Ba, Cu, and Ni may be used. The composite metal hydrate may have the formula MgM_x(OH)_yWherein M is Ca, Al, Fe,Zn, Ba, Cu or Ni, x is 0.1 to 10, and y is 2 to 32. The flame retardant particles may be coated or otherwise treated to improve dispersion and other properties.

An organic flame retardant may be used instead of the inorganic flame retardant, or an organic flame retardant may be used in addition to the inorganic flame retardant. Examples of organic flame retardants include melamine cyanurate, fine particle size melamine polyphosphate, various other phosphorus containing compounds such as aromatic phosphinates, diphosphinates, phosphonates, phosphates, polysilsesquioxanes, siloxanes and halogenated compounds such as hexachloroendomethylenetetrahydrophthalic acid (HET acid), tetrabromophthalic acid, and dibromoneopentyl glycol. Flame retardants (e.g., bromine-containing flame retardants) can be present in an amount of 20phr (parts per 100 parts resin) to 60phr, or 30phr to 45phr, based on the total weight of the resin. Examples of brominated flame retardants include Saytex BT93W (ethylenebistetrabromophthalimide), Saytex 120 (tetradecylborophenoxybenzene), and Saytex 102 (decabromodiphenyl ether).

The flame retardant may be used in combination with a synergist, for example, a halogenated flame retardant may be used in combination with a synergist such as antimony trioxide, and a phosphorus-containing flame retardant may be used in combination with a nitrogen-containing compound such as melamine.

The magnetic particles themselves may increase the flame retardancy of the magneto-dielectric material. For example, the magneto-dielectric material may have improved flame retardancy compared to the same material without the magnetic particles.

The magneto-dielectric material may have improved flammability. For example, the magneto-dielectric material may have a UL94V1 or V0 rating at 1.6 mm.

The magneto-dielectric material may operate at a high operating frequency of 0.5GHz to 10GHz, or 1GHz to 5GHz, or 1GHz to 10GHz, or greater than or equal to 1 GHz.

The magnetic permeability of the magneto-dielectric material, as determined at 1GHz, or 1GHz to 10GHz, may be 1 to 5, or 1 to 3. The magneto-dielectric material may have a low magnetic loss tangent, as determined at 1GHz, of less than or equal to 0.07, or from 0.01 to 0.07, or less than or equal to 0.03, or less than or equal to 0.01, or a low magnetic loss tangent, as determined at 1GHz to 10GHz, of less than or equal to 0.08, or from 0.01 to 0.08.

The magneto-dielectric material may have a low dielectric constant of less than or equal to 35, or less than or equal to 15, or less than or equal to 5 to 30, as determined at 1GHz, or 1GHz to 10 GHz.

The magneto-dielectric material may have a low dielectric loss tangent of less than or equal to 0.005, or less than or equal to 0.001 as determined at 1GHz, or 1GHz to 10 GHz.

Core-shell magnetic particles (also referred to herein simply as magnetic particles) can be prepared by oxidizing outer layers of a plurality of non-oxidized magnetic particles to form a metal oxide shell layer. The oxidizing may include introducing a plurality of non-oxidized magnetic particles to an oxidizing agent, such as oxygen (O)₂) In (1). The oxidizing may include introducing a plurality of non-oxidizing magnetic particles to an oxidizing agent, such as KMnO₃、H₂O₂、K₂Cr₂O₇、HNO₃And the like or combinations thereof. The oxidation of the core may occur at 50 ℃ to 300 ℃ for 2 hours to 14 days. After oxidation, the core-shell particles may be separated from the oxidizing agent and optionally washed, dried, and optionally sieved to select a particle size range.

The core-shell magnetic particles can be prepared by: the core magnetic particles are coated with carbon, heated under reducing conditions to convert the carbon to hydrocarbons, and oxidized to form core-shell magnetic particles.

The polymer matrix may comprise a thermoset polymer or a thermoplastic polymer, including a liquid crystal polymer. The polymer may include polycarbonate, polystyrene, polyphenylene ether, polyimide (e.g., polyetherimide), polybutadiene, polyacrylonitrile, polymethacrylic acid (C)_1-12Alkyl) esters (e.g., Polymethylmethacrylate (PMMA)), polyesters (e.g., poly (ethylene terephthalate), poly (butylene terephthalate), or polythioesters), polyolefins (e.g., polypropylene (PP), High Density Polyethylene (HDPE), Low Density Polyethylene (LDPE), or Linear Low Density Polyethylene (LLDPE)), polyamides (e.g., polyamideimide), polyarylates, polysulfones (e.g., polyarylsulfone or polysulfonamide)) Poly (phenylene sulfide), poly (phenylene ether), polyethers (e.g., poly (ether ketone) (PEK), poly (ether ketone) (PEEK), Polyethersulfone (PES)), polyacrylics, polyacetals, polybenzolsAzoles (e.g. polybenzothiazole or polybenzothiazine phenothiazine), polyOxadiazoles, polypyrazinoquinoxalines, polytetalsuccinimides, polyquinoxalines, polybenzimidazoles, polyhydroxyindoles, polyoxyisoindolines (e.g., polydioxoisoindolines), polytriazines, polypyridazines, polypiperazines, polypyridines, polypiperidines, polytriazoles, polypyrazoles, polypyrrolidines, polycarboboranes, polyoxabicyclononanes, polydibenzofurans, polyphthalamides, polyacetals, polyanhydrides, vinyl polymers (e.g., poly (vinyl ethers), poly (vinyl sulfides), poly (vinyl alcohols), poly (vinyl ketones), poly (vinyl halides) (e.g., polyvinyl chloride), poly (vinyl nitriles) or poly (vinyl esters)), polysulfonates, polysulfides, polyureas, polyphosphazenes, polysilazanes, polysiloxanes, fluoropolymers (e.g., poly (vinyl fluoride) (PVF), poly (vinylidene fluoride) (PVDF), fluorinated ethylene-propylene (FEP), Polytetrafluoroethylene (PTFE) or polyethylene tetrafluoroethylene (PETFE)), or combinations thereof. The polymer may comprise poly (ether ketone), poly (phenylene ether), polycarbonate, polyester, acrylonitrile-butadiene-styrene copolymer, styrene-butadiene copolymer, styrene-ethylene-propylene copolymer, nylon, or combinations thereof. The polymer may comprise high temperature nylon. The polymer may comprise polyethylene (e.g., high density polyethylene). The polymer matrix may include polyolefins, polyurethanes, polyethylenes (e.g., polytetrafluoroethylene), silicones (e.g., polydimethylsiloxane), polyethers (e.g., poly (ether ketone) and poly (ether ketone)), poly (phenylene sulfide), or combinations thereof.

The polymer of the polymer matrix composition may comprise a thermosetting polybutadiene or polyisoprene. As used herein, the term "thermoset polybutadiene or polyisoprene" includes homopolymers and copolymers comprising units derived from butadiene, isoprene, or mixtures thereof. Units derived from other copolymerizable monomers may also be present in the polymer, for example, in grafted form. Copolymerizable monomers include, but are not limited to: vinyl aromatic monomers, for example, substituted and unsubstituted monovinyl aromatic monomers such as styrene, 3-methylstyrene, 3, 5-diethylstyrene, 4-n-propylstyrene, α -methylstyrene, α -methylvinyltoluene, p-hydroxystyrene, p-methoxystyrene, α -chlorostyrene, α -bromostyrene, dichlorostyrene, dibromostyrene, tetrachlorostyrene, and the like; and substituted and unsubstituted divinylaromatic monomers such as divinylbenzene, divinyltoluene, and the like. Combinations comprising copolymerizable monomers may be used. Thermoset polybutadiene or polyisoprene includes, but is not limited to, butadiene homopolymers, isoprene homopolymers, butadiene-vinyl aromatic copolymers such as butadiene-styrene, isoprene-vinyl aromatic copolymers such as isoprene-styrene copolymers, and the like.

Thermosetting polybutadiene or polyisoprene polymers may also be modified. For example, the polymer can be hydroxyl terminated, methacrylate terminated, carboxylate terminated, and the like. Post-reaction polymers such as epoxy-modified, maleic anhydride-modified, or urethane-modified polymers of butadiene or isoprene polymers may be used. The polymer may also be crosslinked, for example, by a divinylaromatic compound (e.g., divinylbenzene), such as polybutadiene-styrene crosslinked with divinylbenzene. Polymers are broadly classified as "polybutadiene" by their manufacturers, such as Nippon Soda Co. and Cray Valley Hydrocarbon specialty Chemicals, Exton, Pa. Mixtures of polymers may also be used, for example, a mixture of polybutadiene homopolymer and poly (butadiene-isoprene) copolymer. Combinations comprising syndiotactic polybutadiene may also be useful.

Curing agents may be used to cure the thermosetting polybutadiene or polyisoprene composition to accelerate the curing reaction. The curing agent may include an organic peroxide, for example, dicumyl peroxide, t-butyl perbenzoate, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, α -di-bis (t-butylperoxy) diisopropylbenzene, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne-3, or a combination thereof. Carbon-carbon initiators may be used, for example, 2, 3-dimethyl-2, 3-diphenylbutane. The curing agent or initiator may be used alone or in combination. The amount of curing agent can be 1.5 weight percent (wt%) to 10 wt% (wt%), based on the total weight of the polymers in the polymer matrix.

The polymer matrix can include a norbornene polymer derived from a monomer composition comprising norbornene monomers, norbornene-type monomers, or a combination thereof.

The polynorbornene matrix can be derived from a monomer composition comprising one or both of norbornene monomers and norbornene-type monomers, and other optional comonomers. The repeating unit derived from norbornene is shown in the following formula (I).

Norbornene-type monomers include tricyclic monomers (e.g., dicyclopentadiene and dihydrodicyclopentadiene); tetracyclic monomers (e.g., tetracyclododecene); and pentacyclic monomers (e.g., tricyclopentadiene); heptacyclic monomers (e.g., tetracyclopentadiene). Combinations thereof may be used. One of the foregoing monomers may be used to obtain a homopolymer or two or more may be combined to obtain a copolymer.

The norbornene-type monomer may include dicyclopentadiene such that the polynorbornene matrix includes repeating units derived from dicyclopentadiene as shown in formula (II) below.

The polynorbornene matrix can include from 50 wt% to 100 wt%, or from 75 wt% to 100 wt%, or from 95 wt% to 100 wt% of repeating units derived from dicyclopentadiene based on the total weight of the polynorbornene matrix.

The norbornene-type monomer may include a functional group such as an alkyl group (e.g., methyl, ethyl, propyl, or butyl), an alkylene group (e.g., ethylene), an aryl group (e.g., phenyl, tolyl, or naphthyl), a polar group (e.g., ester, ether, nitrile, or halogen), or a combination thereof. One example of the norbornene-type monomer having an ethylidene functional group is ethylidene norbornene, as shown in the following formula (III).

The functionalized repeat units can be present in the polynorbornene matrix in an amount from 5 weight percent to 30 weight percent, or from 15 weight percent to 28 weight percent, or from 20 weight percent to 25 weight percent, based on the total weight of the polynorbornene matrix.

The polynorbornene matrix can include less than or equal to 20 weight percent of at least one repeating unit derived from a copolymerizable monomer based on the total weight of the polynorbornene matrix. The copolymerizable monomer may include a monocyclic olefin, a bicyclic olefin, or a combination thereof. The monocyclic olefin and the bicyclic olefin can each independently comprise 4 to 16 carbon atoms, or 4 to 8, or 8 to 12 carbon atoms. The bicyclic olefin may contain 1 to 4 double bonds, or 2 to 3 double bonds. The copolymerizable monomer may include norbornadiene, 2-norbornene, 5-methyl-2-norbornene, 5-hexyl-2-norbornene, 5-ethylidene-2-norbornene, vinylnorbornene, 5-phenyl-2-norbornene, cyclobutene, cyclopentene, cyclopentadiene, cycloheptene, cyclooctene, cyclooctadiene, cyclodecene, cyclododecene, cyclododecadiene, cyclododecatriene, norbornadiene, or a combination comprising at least the foregoing.

The polynorbornene matrix can be formed by Ring Opening Metathesis Polymerization (ROMP) of monomers in the presence of a catalyst system comprising a metathesis catalyst and an activator. The catalyst system may optionally comprise a moderator, a fluorinated compound, a chelating agent, a solvent, or a combination thereof.

The magneto-dielectric material may be formed by injection molding, reaction injection molding, extrusion, compression molding, rolling techniques, and the like. Pastes, greases or slurries of the magneto-dielectric material may be prepared, for example, for use as a coating or sealant. For isotropic magneto-dielectric materials, the magneto-dielectric material may be formed in the absence of an external magnetic field. Conversely, for anisotropic magneto-dielectric materials, the magneto-dielectric material may be formed in the presence of an external magnetic field. The external magnetic field may be 1 kilo-Oe to 20 kilo-Oe.

The magneto-dielectric material may be formed using an injection molding process that includes injection molding a molten magnetic composition comprising a polymer and magnetic particles. A method of forming a magneto-dielectric material can include forming a composition comprising a polymer and magnetic particles; and mixing the composition, wherein the polymer may be melted prior to mixing or after mixing.

The magneto-dielectric material may be prepared by reaction injection molding the thermosetting composition. Reaction injection molding may include mixing at least two streams to form a thermoset composition, and injecting the thermoset composition into a mold, where a first stream may include a catalyst, and a second stream may include an activator. One or both of the first and second or third streams may comprise monomer. One or both of the first and second or third streams may comprise at least one of a cross-linking agent, magnetic particles, and an additive. One or both of the magnetic particles and the additive may be added to the mold prior to injecting the thermosetting composition.

Mixing may occur in the head space of the injection molding machine. Mixing may occur in an in-line mixer. Mixing may occur during injection into the mold. The mixing can occur at a temperature of greater than or equal to 0 ℃ to 200 ℃, or 15 ℃ to 130 ℃, or 0 ℃ to 45 ℃, or 23 ℃ to 45 ℃.

The mold may be maintained at a temperature of greater than or equal to 0 ℃ to 250 ℃, or 23 ℃ to 200 ℃, or 45 ℃ to 250 ℃, or 30 ℃ to 130 ℃, or 50 ℃ to 70 ℃. It may take 0.25 minutes to 0.5 minutes to fill the mold, during which time the mold temperature may decrease. After filling the mold, the temperature of the thermosetting composition may be increased, for example, from a first temperature of 0 ℃ to 45 ℃ to a second temperature of 45 ℃ to 250 ℃. The molding may occur at a pressure of 65 kilopascals (kPa) to 350 kilopascals (kPa). Can be moldedTo occur for less than or equal to 5 minutes, or less than or equal to 2 minutes, or from 2 seconds to 30 seconds. After polymerization is complete, the magneto-dielectric material can be removed at the mold temperature or at a reduced mold temperature. For example, the demolding temperature T_rMay be less than or equal to the specific molding temperature T _m10 ℃ less (T)_r≤T_m-10℃)。

After the magneto-dielectric material is removed from the mold, it may be subsequently cured. The post-curing can occur at a temperature of 100 ℃ to 150 ℃, or 140 ℃ to 200 ℃, for greater than or equal to 5 minutes.

The magneto-dielectric material may be a reinforced magneto-dielectric material, for example comprising glass cloth. The enhanced magneto-dielectric material may be formed by impregnating and laminating a composition comprising a polymer and core-shell magnetic particles onto a reinforcing medium. The reinforcing media may be fibrous, for example, a woven fibrous layer or a non-woven fibrous layer. The reinforcing media may have large pores that allow the composition to substantially impregnate the reinforcing media. The reinforcing medium may comprise glass cloth.

Fig. 6 illustrates a method of forming a magneto-dielectric material starting with the plurality of magnetic particles of step I. Step II illustrates the preparation of core-shell particles. Step II may comprise oxidizing the core with an oxidizing agent to form a shell; preferably, wherein the oxidant comprises oxygen, KMnO₃、H₂O₂、K₂Cr₂O₇、HNO₃Or a combination thereof. Oxidation of the core may occur at 50 ℃ to 300 ℃ for 2 hours to 14 days. After oxidation, the core-shell particles can be separated from the oxidizing agent and optionally washed, dried, and sieved to select a particle size range. Step III illustrates that a plurality of core-shell magnetic particles can be mixed with a polymer to form a mixture. Step IV shows that the mixture can be molded to form a magneto-dielectric material, for example, by compression molding, injection molding, reaction injection molding, or the like. Step V illustrates that the mixture can be impregnated and laminated onto a reinforcement medium (e.g., glass cloth) to form a reinforced magneto-dielectric material.

The magneto-dielectric material may be in the form of an article (e.g., a layer), and further includes a conductive layer (e.g., copper). The thickness of the conductive layer may be 3 to 200 micrometers, or 9 to 180 micrometers. Suitable conductive layers include thin layers of conductive metals such as copper foil currently used to form circuits, e.g., electrodeposited copper foil. The Root Mean Square (RMS) roughness of the copper foil may be less than or equal to 2 microns, or less than or equal to 0.7 microns, wherein the roughness is measured using a Veeco Instruments WYCO optical profiler using white light interferometry.

The conductive layer may be applied by: placing the conductive layer in a mold prior to molding; laminating a conductive layer on the magneto-dielectric material; direct laser structuring; or adhering the conductive layer to the substrate via an adhesive layer. For example, the laminated substrate can include an optional polyfluorocarbon film that can be positioned between the conductive layer and the magneto-dielectric material and a layer of microglass reinforced fluorocarbon polymer that can be positioned between the polyfluorocarbon film and the conductive layer. The layer of microglass-reinforced fluorocarbon polymer can increase the adhesion of the conductive layer to the magneto-dielectric material. The microglass may be present in an amount of 4 wt% to 30 wt%, based on the total weight of the layer. The longest length dimension of the microglass can be less than or equal to 900 micrometers, or from 50 micrometers to 500 micrometers. The microglass may be a type of microglass as is commercially available through Johns-Manville Corporation of Denver, Colorado. Polyfluorocarbon films include fluoropolymers such as PTFE, fluorinated ethylene-propylene copolymers such as TEFLON FEP, or copolymers having a tetrafluoroethylene backbone and fully fluorinated alkoxy side chains such as TEFLON PFA.

The conductive layer may be applied by laser direct structuring. Here, the magneto-dielectric material may contain a laser direct structuring additive, the laser being used to irradiate the surface of the substrate, form a track (track) of the laser direct structuring additive, and apply a conductive metal to the track. The laser direct structuring additive may comprise metal oxide particles (e.g. titanium oxide and copper chromium oxide). The laser direct structuring additive may comprise spinel based inorganic metal oxide particles, such as spinel copper. The metal oxide particles can be coated, for example, with a composition comprising tin and antimony (e.g., 50 to 99 weight percent tin and 1 to 50 weight percent antimony, based on the total weight of the coating). The laser direct structuring additive may comprise 2 to 20 parts of the additive based on 100 parts of the corresponding composition. Irradiation may be performed with a YAG laser having a wavelength of 1064 nm at an output power of 10 watts, a frequency of 80kHz, and a rate of 3 meters per second. The conductive metal may be applied using a plating process in an electroless plating bath containing, for example, copper.

Alternatively, the conductive layer may be applied by adhesively applying the conductive layer. In one aspect, the conductive layer is a circuit (a metallization layer of another circuit), such as a flex circuit. For example, an adhesive layer may be disposed between one or both conductive layers and the substrate. The adhesion layer may comprise poly (arylene ether); and a carboxyl-functionalized polybutadiene or polyisoprene polymer containing butadiene units, isoprene units, or butadiene and isoprene units, and 0 wt% to less than or equal to 50 wt% of co-curable monomer units; wherein the composition of the adhesion layer is different from the composition of the base layer. The adhesive layer may be present in an amount of 2 grams to 15 grams per square meter. The poly (arylene ether) may comprise a carboxyl-functionalized poly (arylene ether). The poly (arylene ether) may be the reaction product of a poly (arylene ether) and a cyclic anhydride, or the reaction product of a poly (arylene ether) and maleic anhydride. The carboxyl-functionalized polybutadiene or polyisoprene polymer may be a carboxyl-functionalized butadiene-styrene copolymer. The carboxyl-functionalized polybutadiene or polyisoprene polymer may be the reaction product of a polybutadiene or polyisoprene polymer and a cyclic anhydride. The carboxyl-functionalized polybutadiene or polyisoprene polymer may be a maleated polybutadiene-styrene or maleated polyisoprene-styrene copolymer. Other methods known in the art may be used to apply the conductive layer as the form of the particular material and circuit material permits, such as electrodeposition, chemical vapor deposition, lamination, and the like.

The conductive layer may be a patterned conductive layer. The magneto-dielectric material may include a first conductive layer and a second conductive layer on opposite sides of the magneto-dielectric material.

The article may comprise a magneto-dielectric material. The article may be an antenna. The article may be a microwave device, such as an antenna or an inductor. The article may be a transformer, antenna, inductor, or anti-electromagnetic interference material. The article may be an antenna, such as a patch antenna, an inverted-F antenna, or a planar inverted-F antenna. The article may be a magnetic bus bar (bus bar), such as a magnetic bus bar for wireless charging; an NFC shielding material; or an electronic bandgap metamaterial.

The magneto-dielectric material may be used in microwave absorbing or microwave shielding applications.

The article may be a multi-frequency article comprising a magneto-dielectric material and a dielectric material, the dielectric material comprising 0 to 2 volume percent magnetic particles based on the total volume of the dielectric material. The dielectric material may comprise the same or different polymer and the same or different filler (e.g., dielectric filler or flame retardant) as the magneto-dielectric material. The multi-frequency article can be used as an antenna in which the dielectric material operates in a first frequency range and the magneto-dielectric material operates in a second frequency range. For example, one of the magneto-dielectric material and the dielectric material may operate at a frequency greater than or equal to a value of 6GHz to 8GHz and the other may operate at a frequency less than the value. The particular values of 6 to 8 may depend on the type of antenna and the tolerance of the losses in the antenna.

Fig. 5 is an illustration of a top view of a multi-frequency magneto-dielectric material with a first conductive layer 20 disposed on top of a magneto-dielectric substrate 10 and a dielectric substrate 30. Fig. 5 illustrates that the first conductive layer 20 may be asymmetric with respect to the magneto-dielectric substrate 10 and the dielectric substrate 30. Conversely, the first conductive layer 20 may be symmetrical with respect to the magneto-dielectric substrate 10 and the dielectric substrate 30. For example, a conductive layer may be patterned on each of the magneto-dielectric and dielectric substrates based on the desired radiation frequency and substrate characteristics to resonate and radiate within a desired frequency range. The multi-frequency magneto-dielectric material may be formed by a two-shot injection molding process (e.g., a two-shot injection molding process in which a thermoplastic material or a thermoset material is reaction injection molded) that includes a first injection molding of one of the magneto-dielectric material and the dielectric material and then a second injection molding of the second of the magneto-dielectric material and the dielectric material.

The following examples are provided to illustrate the present disclosure. These examples are merely illustrative and are not intended to limit devices made in accordance with the present disclosure to the materials, conditions, or process parameters set forth therein.