Process for preparing ferrite magneto-dielectric materials for VUHF applications

Abstract

Process for preparing ferrite magnetodielectric materials for VUHF application The present invention relates to a process for preparing a ferrite material, said process comprising the following steps: a step S1 of grinding ferrite particles P1 with grinding balls B1, to obtain ferrite particles P2, the diameter d90 of the ferrite particles P2 being less than the diameter d90 of the particles P1, said step S1 being carried out at an energy E1 greater than 1.5 kWh / kg and a step S2 of grinding the ferrite particles P2 with grinding balls B2, to obtain ferrite particles P3, the diameter d90 of the ferrite particles P3 being less than the diameter d90 of the particles P2, said step S2 being carried out at an energy E2 greater than 5 kWh / kg, and the diameter of the balls B1 being greater than the diameter of the balls B2.The invention also relates to a ferrite magneto-dielectric material obtained by such a process, intended for use in the VUHF frequency band. Figure for the abstract: none.

Description

Title of the invention: Process for preparing ferrite magnetodielectric materials for VUHF application

[0001] The present invention relates to a process for preparing a ferrite magnetodielectric material from ferrite particles. It also relates to a ferrite magnetodielectric material thus obtained. Such a material can be used in the field of communications for the manufacture of antennas, in particular adapted to operate in the very high frequency (VHF) band, between 30 MHz and 300 MHz, and the ultra high frequency (UHF) band, between 300 MHz and 3 GHz, or VUHF.

[0002] In the field of communications, antenna miniaturization is a major challenge, especially for antennas operating below 1 GHz. Indeed, the size of an antenna is directly proportional to the wavelength of the transmitted / received signal, which is on the order of one meter for VHF / UHF frequencies (VHF: 30 MHz to 300 MHz; UHF: 300 MHz to 3000 MHz). Therefore, reducing the size of an antenna whose frequency corresponds to a high wavelength, particularly one on the order of one meter, is not straightforward.

[0003] Among the various strategies employed to produce a miniature antenna (i.e., small compared to the wavelength), a commonly used one consists of using the dielectric properties of a material in order to concentrate the fields in a smaller volume. The use of a dielectric material with a high dielectric constant (e') allows a significant reduction in the size of the antennas but is accompanied by a significant decrease in performance (radiation efficiency, bandwidth) (RK Mongia, A. Ittipiboon, and M. Cuhaci, “Low profile dielectric resonator antenna using a very high permittivity material,” Electron. Lett., Vol 30 N°17 (1994) 1362-1663).

[0004] It has been shown in recent years that the use of magnetic materials with high permeability makes it possible to circumvent this limitation. Indeed, the use of materials such as ferrites with high magnetic permeability (p') makes it possible to reduce the size of antennas while maximizing their efficiency. In fact, although e' has a positive impact on dielectric losses and the amount of stored energy, it has been proven that e' also has a negative impact on the bandwidth and efficiency of the antenna, and that p' has the opposite effect, i.e., a positive impact on these two parameters (MAC Niamien, S. Collardey, A. Sharaiha, K. Mahdjoubi, "Compact Expressions for Efficiency and Bandwidth of Patch Antennas Over Lossy Magneto-Dielectric Materials", IEEE antennas and wireless propagation letters, 10 (2011) 63-66). Another considerable advantage is that if the antenna is kept at the same dimensions, such a material would increase the antenna's performance.

[0005] In the VUHF frequency bands, ferrites usually exhibit high magnetic losses, making them unusable for this application. However, it has been shown that it is possible to reduce these losses by synthesizing these ferrites from powders obtained by co-precipitation and sintering at low temperature (i.e., below 1000°C) (A. Saini, K. Rana, A. Thakur, P. Thakur, JL. Mattéi, P. Queffelec, “Low loss Composite nano ferrite with matching permittivity and permeability in UHF band”, Materials Research Bulletin, 76, p. 94-99 (2016)). This process allows the production of nanoparticles, which, once sintered at low temperature to prevent grain growth, allow the manufacture of ferrites whose microstructure is also nanometric.This would allow us to approach a single-magnetic-domain grain configuration and avoid the contribution of magnetic walls to permeability (magnetic losses are then limited). However, this coprecipitation process can be complex and expensive to implement industrially.

[0006] For these reasons, the present invention aims to provide a method for preparing a material enabling the manufacture of miniature antennas suitable for use in VHF and / or UHF frequency bands.

[0007] In particular, the present invention aims to provide a method for preparing a ferrite magneto-dielectric material exhibiting low magnetic losses in the VHF and / or UHF frequency bands.

[0008] The present invention aims in particular to provide such a preparation process which is less cumbersome and less costly to implement from an industrial point of view than current processes.

[0009] The invention therefore relates to a process for preparing a ferrite magneto-dielectric material, said process comprising the following steps:

[0010] a step Si of grinding ferrite particles Pi with grinding balls Bb to obtain ferrite particles P2,

[0011] the diameter d90 of the P2 ferrite particles being less than the diameter d90 of the Pb particles

[0012] said step SI being carried out at an energy Ei greater than 1.5 kWh / kg, preferably greater than 2 kWh / kg, preferably greater than 2.5 kWh / kg, preferably greater than 3 kWh / kg, and

[0013] a step S2 of grinding the ferrite particles P2 with grinding balls B2, to obtain ferrite particles P3,

[0014] the diameter d90 of the ferrite particles P3 being less than the diameter d90 of the particles P2,

[0015] said step S2 being carried out at an energy E2 greater than 5 kWh / kg, preferably greater than 5.5 kWh / kg, preferably greater than 6 kWh / kg,

[0016] and the diameter of the balls Bi being greater than the diameter of the balls B2.

[0017] Preferably, the process according to the invention is a wet process.

[0018] By ferrite particles, we mean particles composed of iron(III) oxide and of one or more metal oxides.

[0019] Preferably, in the process according to the invention, the ferrite particles Pi comprise, preferably, iron oxide (Fe2O3) particles and one or more oxides selected from nickel oxide (NiO), cobalt oxide (CoO), zinc oxide (ZnO), manganese oxide (MnO), and copper oxide (CuO). The ferrite particles Pi preferably all have the same oxide composition.

[0020] According to the process of the invention, the grinding of the Si and S2 stages is carried out in mills.

[0021] By energy E, we mean the effective energy transferred from the mill to the particles during the milling steps, which is defined as follows:

[0022] E=£n^text

[0023] with Enette the net energy which corresponds to the gross energy supplied to the crusher less the energy consumed by this crusher when it is running idle,

[0024] m the mass of particles in the mill chamber, and

[0025] t the duration of the grinding.

[0026] In the description that follows, the energy Ei will refer to the effective energy E of the grinding step Si and the effective energy E2 to that of the grinding step S2.

[0027] The "diameter" of a PH P2 or P3 ferrite particle is defined as the "equivalent volumetric spherical diameter". The equivalent volumetric spherical diameter corresponds to the result of measuring the size of said particle using the laser scattering particle size distribution technique described below.

[0028] By "diameter d 90", it is understood that 90% of the particles, by volume, have an equivalent spherical diameter of value less than or equal to the value of d90.

[0029] By "diameter d 5 0", it is meant that 50% of the particles, by volume, have an equivalent spherical diameter of value less than or equal to the value of d50.

[0030] By "diameter dio", it is understood that 10% of the particles, by volume, have an equivalent spherical diameter of value less than or equal to the value of di0.

[0031] The diameter values ​​d90, d50, and di0 were obtained by laser scattering particle size distribution (LSPD) analysis. As an example of such an analysis, it can be performed on an aqueous suspension of particles using a Malvern Mastersizer 3000 LSPD analyzer. For the particle size distribution analyses according to the invention, samples (approximately 5 mL) of the aqueous suspensions of ferrite powder were taken with a pipette at the end of the grinding cycle.For the measurement, a small portion of the freshly collected sample at the end of the grinding cycle was introduced drop by drop into the Hydro MV measuring accessory chamber of the Malvern model Mastersizer 3000 equipment, containing deionized water. After each drop was introduced, the obscuration value stabilized, reaching a value around 5% (the decrease in the laser energy level received by the detector due to the introduction of particles into the measuring cell relative to the incident laser energy level). The equipment settings used for the measurement are: - Suspension stirring speed: 2000rpm - Ultrasound: 0% - Refractive index of particles: 2.360 - Particle absorption index: 1,000 - Refractive index of particles in blue: 2.360 - Particle absorption index in the blue: 1.000 - Refractive index of the dispersant (water): 1.330 - Diffraction model: Mie - Analysis model: general - Analysis sensitivity: normal Obtaining PI ferrite particles

[0032] In order to obtain the Pb ferrite particles, the raw materials in powder form of oxides and / or carbonates are first selected according to the desired composition of the magneto-dielectric ferrite material. For example, the following oxides and carbonates are selected: Fe2O3, Co3O4, NiO, ZnO, CuCO3·xH2O, MnCO3.

[0033] Preferably, these oxides and / or carbonates in powder form are weighed, then simultaneously mixed and ground to form intimately mixed oxide and / or carbonate powders.

[0034] Preferably, the mixing and grinding of the selected oxides and / or carbonates are carried out simultaneously in aqueous mode by / in a ball mill, a jar turner or an attrition mill.

[0035] For example, grinding in a ball mill or in a jar mill containing steel grinding elements (balls) takes place for a period of between 15 and 25 hours, preferably between 18 and 22 hours. In particular, grinding takes place for 20 hours.

[0036] Preferably, the oxide and / or carbonate powders thus obtained are then subjected to a calcination step, where the mixed and ground oxide and / or carbonate powder is heated to a high temperature to allow the decomposition of the carbonates and the chemical reactions between the oxides to form the desired ferrite phase. In other words, the Pi ferrite particles are preferably obtained by a calcination step of oxide and / or carbonate powders. Advantageously, the calcination is carried out at a temperature between 800°C and 1100°C. Advantageously, the calcination is carried out for a duration of 2 to 4 hours.Thus, according to a preferred embodiment, the process includes a step for obtaining Pi ferrite particles such that: the PI ferrite particles are obtained by a calcination step of oxide and / or carbonate powder, said calcination step being carried out preferably at a temperature ranging from 800°C to 1100°C and preferably for a duration ranging from 2h to 4h.

[0037] The particles obtained at the calcination output may optionally undergo a second grinding, in order to obtain Pb ferrite particles

[0038] This grinding is preferably wet grinding in a ball mill or a rotary mill with steel balls. In particular, this grinding takes place for a period of between 30 and 40 hours, preferably between 34 and 38 hours. The second grinding can optionally be carried out in an attrition mill.

[0039] The ferrite particles thus obtained are the Pi ferrite particles. Advantageously, the diameter d90 of the Pi particles is less than 50 µm, preferably less than 40 µm, and preferably less than 30 µm. According to one embodiment, the diameter d90 of the Pi particles is from 10 µm to 50 µm. Preferably, the Pi ferrite particles have a specific surface area of ​​at least 2 m² / g, preferably at least 2.5 m² / g, and preferably at least 3 m² / g.

[0040] By "specific surface area", we mean the ratio of the total surface area of ​​all the particles (in m2) to the total mass of all said particles (in grams).

[0041] The specific surface area of ​​the particle powders was measured by the BET (Brunauer, Emmett and Teller Method) using the Micromeritics FlowSorb II 2300 equipment. According to the BET method, the specific surface area of ​​a powder is calculated from the volume of a gas, in this case a 70% He - 30% N2 mixture, which is adsorbed onto the surface of a known mass of this powder during the measurement. For the Sample preparation for specific surface area measurements: 5 g of ferrite powder (Pb P2 or P3, respectively obtained from drying suspensions after grinding, and after calcination of the raw materials Si and S2) were placed in an oven at 110°C overnight to eliminate all moisture. For the measurement, a clean, dry measuring cell was weighed before and after being filled with 5 g of P2 or P3 particle powder and placed in the degassing compartment of the measuring equipment. The powder was held there at 250°C for 30 minutes to eliminate any residual moisture and any other gas molecules adsorbed onto the powder surface before measurement. The measuring cell was then transferred to the measurement location. After equipment calibration, the measurement was performed. The crushing

[0042] The process according to the invention comprises two stages Si and S2 of grinding ferrite particles Pi and P2, respectively. Preferably, the grinding of the Pi particles in stage Si is a high-energy grinding. Preferably, the grinding of the P2 particles in stage S2 is a high-energy grinding. Advantageously, both the grinding of the Pi particles in stage Si and the grinding of the P2 particles in stage S2 are high-energy grindings.

[0043] High-energy grinding is a grinding process that allows the preparation of nanostructured materials.

[0044] "High energy" means a net energy transmitted to the grinding medium greater than 1.5 kWh / kg during the grinding stage.

[0045] According to the process of the invention, the high-energy grinding in steps S1 and S2 consists of agitating the ferrite particles P1 and P2, respectively, with grinding balls in a sealed chamber. Under the effect of collisions and / or friction, the ferrite particles fracture to form smaller particles. During the collisions and / or friction of the balls on the ferrite particles P1 or P2, there is indeed a transfer of kinetic energy from the grinding balls to the ferrite particles, resulting in fracturing and a reduction in particle size.

[0046] The grinding stages Si and S2 are characterized by the energy E, respectively energies E and E2, which corresponds to the energy transferred from the grinder to the particles:

[0047] E=

[0048] with Enette the net energy which corresponds to the gross energy supplied to the mill less the energy consumed by this mill when it operates at idle,

[0049] m the mass of particles in the mill enclosure, and

[0050] t the duration of the milling.

[0051] Advantageously, the grinding of stages Si and S2 is carried out with an attrition mill under conditions that maximize the transfer of energy from the mill to the effective reduction of particle size.

[0052] In addition, the mill filling rate represents the volume occupied by the grinding elements (balls) in relation to the total volume of the mill enclosure.

[0053] Preferably, the grindings of stages Si and S2 independently have a filling rate of less than 75%, preferably less than 70%, preferably less than 65%.

[0054] Advantageously, the grinding beads Bi and B2 used respectively for the grinding steps Si and S2 are zirconium oxide beads. In particular, the beads Bi and B2 are zirconium oxide, or zirconia, beads with the formula ZrO2. Preferably, the beads Bi and B2 are yttrium oxide-stabilized zirconia beads. Step SI

[0055] The process according to the invention includes a step Si of grinding ferrite particles Pi with grinding balls B, to obtain ferrite particles P2.

[0056] Preferably, the grinding of step Si is a high-energy grinding as defined above. In particular, the grinding of step Si is carried out at an energy Ei greater than 1.5 kWh / kg, preferably greater than 2 kWh / kg, preferably greater than 2.5 kWh / kg, preferably greater than 3 kWh / kg.

[0057] Advantageously, the grinding of the Si step is carried out for a period of 2h to 10h and preferably from 3h to 8h.

[0058] Preferably, the grinding of step Si is carried out with an attrition mill, preferably an attrition mill containing accelerating elements in the grinding chamber. Preferably, said accelerating elements may be of the DYNO®-ACCELERATOR type. For example, the DYNO MILL ECM AP 05 mill manufactured by WAB Group can be used for grinding ferrite particles Pi.

[0059] The diameter of the grinding balls Bi which are used in step Si is preferably between 0.3 mm and 1 mm, preferably between 0.3 mm and 0.8 mm, preferably between 0.3 mm and 0.6 mm.

[0060] According to an advantageous embodiment, during the SI grinding step, the PI ferrite particles are in suspension. According to this embodiment, the PI ferrite particle suspension preferably comprises PI ferrite particles and deionized water; preferably, the PI ferrite particles are present at a concentration of approximately 1.6 kg per liter of deionized water.

[0061] According to such an embodiment, the process may include adding a dispersing agent to the suspension containing the Pi particles before the grinding in step Ep. The dispersing agent advantageously prevents the agglomeration of the particles. ferrite disperses as the size of the particles is reduced. The dispersing agent thus maintains a sufficiently low viscosity in the suspension to ensure efficient grinding, even when the suspension has a high concentration of ferrite particles. In other words, a dispersing agent can be added to the aqueous suspension containing the Pi particles so that the mill chamber used in step Si contains the aqueous suspension of Pb particles, the grinding media Bi, and a dispersing agent.

[0062] In particular, the dispersing agent is a polyelectrolyte polymer. The dispersing agent is preferably an alkali-free carboxylic acid preparation, for example Dolapix CE64 (Zschimmer & Schwarz GmbH Co., DE).

[0063] When present, the dispersing agent preferably represents 0.5 to 4%, preferably 1 to 3%, and most preferably 1.5 to 2.5% of the mass of the aqueous suspension containing the Pp particles

[0064] Thus, according to one embodiment, during the SI grinding step, the PI ferrite particles are in suspension, preferably in suspension in water. Advantageously, the suspension further comprises a dispersing agent, preferably chosen from polyelectrolyte polymers, more preferably carboxylic acids.

[0065] The grinding of the Si step allows obtaining P2 ferrite particles.

[0066] The diameter d90 of the P2 particles is less than the diameter d90 of the Pb particles

[0067] Preferably, the diameter d90 of the P2 particles is less than 1.5 µm, preferably less than 1.0 qm, preferably less than 0.8 qm. Step S2

[0068] The process according to the invention includes a step S2 of grinding ferrite particles P2 with grinding balls B2, to obtain ferrite particles P3.

[0069] Preferably, the grinding in step S2 is a high-energy grinding as defined above. In particular, the grinding in step S2 is carried out at an energy E2 greater than 5 kWh / kg, preferably greater than 5.5 kWh / kg, preferably greater than 6 kWh / kg.

[0070] Advantageously, the grinding of step S2 is carried out for a period of 2h to 10h, and preferably from 3h to 8h.

[0071] Preferably, the grinding of step S2 is carried out with an attrition mill, preferably an attrition mill containing accelerating elements, preferably of the DYNO®-ACCELERATOR type, in the grinding chamber.

[0072] For example, the DYNO MILL ECM AP 05 mill manufactured by WAB Group can be used for grinding P2 ferrite particles.

[0073] The diameter of the grinding balls B2 which are used in step S2 is preferably less than 0.3 mm, preferably less than 0.2 mm, preferably less than or equal to 0.1 mm.

[0074] According to one embodiment, the diameter of the balls Bi is strictly greater than the diameter of the balls B2.

[0075] According to one embodiment, during the grinding step S2, the ferrite particles P2 are in suspension, preferably in suspension in water. Advantageously, the suspension further comprises a dispersing agent, preferably chosen from polyelectrolyte polymers, more preferably carboxylic acids.

[0076] According to such an embodiment, the process therefore includes the addition of a dispersing agent to the aqueous suspension containing the particles P2 before the grinding in step S2. In other words, a dispersing agent can be added to the aqueous suspension containing the particles P2 so that the mill enclosure in step S2 comprises the aqueous suspension of particles P2, the grinding beads B2, and a dispersing agent.

[0077] In particular, the dispersing agent is a polyelectrolyte polymer. The dispersing agent is preferably a preparation comprising carboxylic acid, advantageously alkali-free carboxylic acid, for example Dolapix CE64 (Zschimmer & Schwarz GmbH Co., DE).

[0078] When present, the dispersing agent preferably represents between 0.1 and 3%, preferably between 0.3 and 2.5%, most preferably between 0.5 and 2% of the mass of the aqueous suspension containing the P2 particles.

[0079] The grinding in step S2 allows obtaining P3 ferrite particles.

[0080] The diameter d90 of the P3 particles is less than the diameter d90 of the P2 particles.

[0081] Preferably, the diameter d90 of the P3 particles is less than 200 nm, preferably less than 150 nm, preferably less than 120 nm.

[0082] Preferably, the diameter d50 of the P3 particles is less than 100 nm, preferably less than 80 nm and / or the diameter di0 of the P3 particles is less than 60 nm, preferably less than 50 nm.

[0083] Advantageously, the P3 particles have a specific surface area of ​​at least 20 m2 / g, preferably of at least 30 m2 / g, preferably of at least 40 m2 / g, preferably of at least 60 m2 / g, preferably of at least 70 m2 / g.

[0084] Preferably, the process according to the invention makes it possible to obtain a volume of at least 60%, preferably at least 75%, preferably at least 85% of P3 particles having a diameter less than 100 nm, relative to the total volume of P3 particles obtained. Additional steps

[0085] According to one embodiment, the process according to the invention further comprises at least one step of shaping the particles P3 following the step S2, into solid material.

[0086] Thus, according to one embodiment of the process, step S2 is followed by a pressing step, preferably uniaxial pressing and / or isostatic pressing, of the ferrite particles P3.

[0087] Advantageously, the pressing step is preceded by a coating or atomization step of the ferrite P3 particles to improve the behavior of the P3 particle powder during the pressing step. According to this embodiment, the process according to the invention therefore comprises:

[0088] _ a step SI of grinding ferrite particles PI with grinding balls Bl, to obtain P2 ferrite particles,

[0089] the diameter d90 of the P2 ferrite particles being less than the diameter d90 of the PI particles,

[0090] said step SI being carried out at an energy El greater than 1.5 kWh / kg, preferably greater than 2 kWh / kg, preferably greater than 2.5 kWh / kg, preferably greater than 3 kWh / kg, and

[0091] _ a step S2 of grinding the ferrite particles P2 with grinding balls B2, to obtain P3 ferrite particles,

[0092] the diameter d90 of the ferrite particles P3 being less than the diameter d90 of the particles P2,

[0093] said step S2 being carried out at an energy E2 greater than 5 kWh / kg, preferably greater than 5.5 kWh / kg, preferably greater than 6 kWh / kg,

[0094] and the diameter of the balls Bl being greater than the diameter of the balls B2;

[0095] - a step of coating or atomizing the P3 ferrite particles; and

[0096] - a pressing step, preferably uniaxial pressing and / or a pressing isostatic, coated or atomized P3 ferrite particles.

[0097] Preferably, the step of shaping the P3 particles into solid material is done by pressing.

[0098] Preferably, the pressing performed is uniaxial pressing. Alternatively, uniaxial pressing is followed by isostatic pressing. The pressing allows the P3 ferrite particles to be shaped into a material. The material is preferably in the form of plates, discs, cylinders, or tori.

[0099] Advantageously, the process according to the invention includes a step of coating or atomizing the P3 particles before shaping them. This coating step The coating or atomization step is advantageously carried out with the addition of binder(s) and / or plasticizer(s). Preferably, the binder is a polyvinyl alcohol (PVA), for example, OPTAPIX PAF 35. Preferably, the plasticizer is a polyethylene glycol, for example, PEG 400. The coating or atomization step, as well as the binder(s) and / or plasticizer(s) used in this step, are well known to those skilled in the art. Binders and plasticizers are organic agents typically used to improve the behavior of a ceramic powder in the pressing step (filling molds with the powder, refining granules during pressing, reducing the pressure required to obtain a given part density after pressing, increasing the strength of the pressed part, etc.). Such behavior is particularly important in an industrial pressing process and / or for the manufacture of large parts.

[0100] According to one embodiment, the step of pressing the P3 ferrite particles is further followed by a heat treatment of the material thus formed.

[0101] In particular, the heat treatment of the shaped material is sintering. Preferably, the sintering is carried out at a holding temperature ranging from 800°C to 1000°C. Advantageously, the sintering is carried out at a temperature ranging from 800°C to 900°C, and more advantageously, from 800°C to 850°C.

[0102] Typically, sintering is carried out under an oxidizing atmosphere, for example in air.

[0103] In particular, the sintering includes a step-by-step heating period ranging from 175°C to 375°C, each stage lasting between 1 and 48 hours. These stages between 175°C and 375°C are used to burn off and eliminate organic components such as dispersants, binders and / or plasticizers that may have been introduced during the grinding, coating and / or atomization of the ferrite particles. Material obtained

[0104] The process according to the invention makes it possible to obtain a ferrite magneto-dielectric material.

[0105] Preferably, the material obtained has a relative dielectric permittivity er greater than 1 and / or a relative magnetic permeability pr greater than 1. Preferably, the process according to the invention makes it possible to obtain a ferrite magneto-dielectric material with a dielectric permittivity er between 3 and 30, preferably between 6 and 22 and a magnetic permeability pr between 2 and 40, preferably between 4 and 30.

[0106] The term "relative dielectric permittivity, er" means the resistance of a material to produce an electric field (er = e / e0, where e is the permittivity of the material and e0 is a constant and corresponds to the permittivity of free space).

[0107] The dielectric permittivity is preferably evaluated on the basis of perturbation theory, applied to a rectangular cavity.

[0108] The method for analyzing the dielectric permittivity is preferably as follows.

[0109] The setup used for the analysis consists of the following elements: 10MHz - 26.5GHz HP8340A synthesizer, 22.92 x 10.20 x 90.02 cavity with 8235MHz open-circuit resonance frequency The Wave Solution PS-16-SBB-402-402-B-M90 in silver-plated brass with UBR100 flanges, 10MHz - 26.5GHz HP85025B detector, HP8757A scalar analyzer.

[0110] The measurement cavity is formed from a section of standardized "WR90" waveguide (internal cross-section WR90 = 22.92 x 10.20 mm²), closed at the ends by plates with 4 mm diameter holes. It is coupled via the holes at the input to the synthesized HF microwave source, and at the output to the detector for the analyzer. A sample of the sintered and machined material, in the form of a circular rod with a constant cross-section and a diameter of ~1 mm, previously baked between 150°C and 200°C for at least 30 min, is introduced into its center at the maximum of the HF electric field. The measurement is performed at a frequency band around the resonance frequency of the empty cavity, 8235 MHz. The frequency and width of the resonance peak at half maximum are measured with the measurement cavity empty and then with the rod present.The relative dielectric permittivity, er, is calculated from the resonance frequency values, measured with the vacuum cavity and the cavity containing the sample, and from the volume of the cavity and that of the bar sample used for the measurement in the cavity.

[0111] The term “relative magnetic permeability, pr” means the ability of a material to conduct magnetic flux relative to a vacuum (pr = p / po, where p is the magnetic permeability of the material and po is a constant and represents the magnetic permeability of a vacuum).

[0112] The application of a magnetic flux created by an alternating electric current generates a magnetic flux and magnetic losses in a magnetic material. The permeability of a magnetic material under a magnetic flux created by an alternating electric current is defined as the complex relative magnetic permeability pr* of which:

[0113] pr* = pr'- i pr”

[0114] where

[0115] pr' is the real part of the complex relative magnetic permeability, related to the energy stored in the material by the application of the magnetic flux created by an alternating electric current

[0116] pr” is the imaginary part of the complex relative magnetic permeability, which corresponds to the energy dissipated in the material by different mechanisms due to the application of the magnetic flux created by an alternating electric current (magnetic losses)

[0117] and i is an imaginary number whose square has the value -1

[0118] In particular, the process according to the invention makes it possible to obtain a ferrite magnetodielectric material exhibiting low magnetic losses at frequencies between 1 and 1000 MHz. By low magnetic losses, it is understood that the loss tangent tan ôp is less than 0.1. The loss tangent is defined as: tan ôp = pr” / pr'.

[0119] The relative magnetic permeability pr and the magnetic loss tangent tan ôp were obtained using a Keysight model E4991B impedance analyzer from the inductance and impedance values ​​measured in a coaxial cell mounted without and with the magnetic material (inductance method) in a frequency band from 1MHz to 1000MHz on toroidal samples in APC7 format (0ext7 x 0int3) manufactured by the process according to the invention.

[0120] Preferably, tan ôp is less than 0.1 over the frequency band from 1 to 1000 MHz, preferably from 1 to 600 MHz, preferably from 1 to 590 MHz, preferably from 1 to 250 MHz, preferably from 1 to 200 MHz, and preferably from 1 to 160 MHz. Advantageously, tan ôp is less than 0.08, preferably less than 0.06, and preferably less than 0.05 over the frequency band from 1 to 150 MHz.

[0121] A ferrite material obtained by the process according to the invention is for example usable as an antenna material on VUHF frequency bands, in particular on a frequency range from 1 to 1000 MHz, preferably from 1 to 800 MHz, preferably from 1 to 600 MHz, preferably from 1 to 590 MHz, preferably from 1 to 250 MHz, preferably from 1 to 200 MHz, preferably from 1 to 160 MHz.

[0122] According to one embodiment, the process according to the invention further makes it possible to obtain a ferrite material having a microstructure whose grain size is less than 200 nm, preferably less than 150 nm, preferably less than 120 nm, preferably less than 100 nm.

[0123] Preferably, the grain size of the sintered ferrite material is obtained by Electron Backscattered Diffraction (EBSD) image analysis of the material's microstructure performed by Scanning Electron Microscopy (SEM). EBSD is a widely used technique for characterizing the microstructure and local crystallographic texture of polycrystalline materials. Scanning Electron Microscopy allows for the observation and acquisition of information about the surface of a material by The processing involves the radiation generated by the interaction of the material with a beam of accelerated electrons emitted by the Scanning Electron Microscope. Specifically, the radiation analyzed to generate the orientation map image corresponds to the backscattered electrons produced by the diffraction of an electron beam that struck the material at a relatively steep angle. Software then calculates the crystalline orientation of the material from the diffraction pattern (Kikuchi pattern) and generates a map where each grain or crystallite is represented by a color. This map provides information such as grain size and distribution to form the microstructure of the material.

[0124] Advantageously, the process according to the invention makes it possible to obtain a ferrite material having the following composition:

[0125] NiaZnbCucCodMneFe2_ôO4

[0126] with:

[0127] 2(a+b+c+d+e) + 3(2-ô) = 8

[0128] 0.05 < b < 0.5

[0129] 0 < c < 0.25

[0130] 0.005 < d < 0.25

[0131] 0 < e < 0.1

[0132] 0 < ô < 0.08.

[0133] The invention also relates to a ferrite material obtained by the process described above. Such a material is particularly useful in VHF, UHF and / or VUHF antennas.

[0134] Advantageously, the antenna is adapted for operation between 1 to 1000 MHz, preferably from 1 to 800 MHz, preferably from 1 to 600 MHz, preferably from 1 to 590 MHz, preferably from 1 to 250 MHz, preferably from 1 to 200 MHz, preferably from 1 to 160 MHz. Description of the figures

[0135] [Fig. 1] Figure 1 is a graph representing magnetic permeability and magnetic losses as a function of frequency in MHz for different materials:

[0136] - Curves 1 and 1' represent respectively the magnetic losses ("tanô - sintering at 900°C, high energy process according to the invention") and the magnetic permeability ("p' - sintering at 900°C, high energy process according to the invention") of a material obtained according to the process of Example 2 and sintered at a temperature of 900°C.

[0137] - Curves 2 and 2' represent respectively the magnetic losses ("tanô - sintering 850°C, high energy process according to the invention") and the magnetic permeability ("p' - sintering 850°C, high energy process according to the invention") of a material obtained according to the process of Example 2 and sintered at a temperature of 850°C.

[0138] - The other curves represent magnetic losses and permeability magnetic material obtained using a comparative low-energy process and sintered at different temperatures (from darkest to lightest: 1180, 1140 and 1100 °C).

[0139] [Fig.2] Fig.2 is a graph representing the magnetic permeability and the magnetic losses as a function of frequency in MHz for the material obtained according to the process of Example 3. Examples

[0140] Example 1: Grinding process outside the invention

[0141] The following raw materials are selected and weighed according to Table 1:

[0142] [Tables 1] Raw materials Mass (g) Fe2O3 1905.66 NiO 587.07 ZnO 353.03 CuCO3.xH2O 70.21 MnC03 75.82 Co3O4 8.21

[0143] Preparation of ferrite particles

[0144] The protocol is as follows:

[0145] - 3.0 ± 0.1 kg of raw materials as detailed in Table 1 are weighed and placed in an 8L jar of a jar-turning crusher (A. Faure Type 28V30-11) containing 11.4 kg of 100C6 steel balls (supplied by Maridt GmbH) of various diameters and in the approximate quantities shown in Table 2;

[0146] - 3.3 ± 0.1 L of deionized water and 20 ± 2 g of Dolapix CA dispersant supplied by Zschimmer & Schwarz GmbH Co., DE are added,

[0147] - the grinding is carried out over a period of 20 hours,

[0148] - the resulting suspension is then dried at 200°C for 4 to 6 hours and then at 120°C for about 14 to 16 hours until the humidity level is < 0.2% (measured in a THOMAS ASHWORTH SPEEDY MOISTURE TESTER).

[0149] - the powder is then subjected to a calcination step, at a temperature of 1050°C for 3 hours, then

[0150] - the particles obtained at the calcination outlet are ground for a period 36 hours in a jar grinder under the same conditions as the first grinding, except for the addition of the dispersant (no dispersant added).

[0151] Approximate diameters and quantities of 100C6 steel balls used in grinding raw materials for the preparation of ferrite particles:

[0152] [Tables2] Diameter (mm) Ball mass (kg) 27 to 32 6.6 13 to 15 2.1 9 to 10 2.7

[0153] The ferrite particles obtained have a specific surface area between 2 m2 / g and 4 m2 / g, a diameter d90 of about 30 pm, and have the following composition: Ni0.602Zn0.34Cu0.05Co0.00sMn0.05Fe1.95O4.

[0154] Grinding of ferrite particles:

[0155] The ferrite particles obtained above are ground by a steam jet mill, under the reference Steam jet mill s-jet 25 of the Netzsch brand.

[0156] The grinding is carried out with the following parameters:

[0157] - Dynamic separator speed: 10000 rpm

[0158] - Grinding air pressure: 7 bar

[0159] - Flow rate: 59 m3 / h

[0160] The particles thus obtained are observed by Scanning Electron Microscopy (SEM) with the JEOL JSM-IT200 equipment in Backscattered Electron (BSE) mode with an accelerating voltage of 5kV, WD (Working Distance) 10 mm. The observed particles have a diameter on the order of Ipm according to the visual analysis of the image.

[0161] Example 2: Grinding process according to the invention

[0162] Preparation of ferrite particles:

[0163] The protocol for preparing the ferrite particles and their composition are the same as those in Example 1.

[0164] The PI ferrite particles thus obtained therefore have a specific surface typically between 2 m2 / g and 4 m2 / g, a diameter d90 of about 30 pm, and have the following composition: Ni0.602Zn0.34Cu0.05Co0.00sMn0.05Fe1.95O4.

[0165] Grinding of ferrite particles:

[0166] The PI ferrite particles obtained above are ground in two stages by an attrition mill under the reference DYNO MILL ECM AP 05 of the brand WAB Group.

[0167] First step S1:

[0168] - the PI ferrite particles are suspended in aqueous slip, typically at a rate of approximately 1.6 kg of ferrite powder per liter of deionized water,

[0169] - 2% by weight relative to the total weight of the dispersing agent slurry (Dolapix CE64) are added to the slip,

[0170] - the slip is ground for 4 hours with yttria zirconium oxide beads 0.3 mm in diameter, with the following parameters:

[0171] - crusher speed: 12 m / s

[0172] - energy El between 1.8 and 2.1 kWh / kg

[0173] At the end of the SI step, P2 ferrite particles are obtained.

[0174] Second stage S2:

[0175] - 0.8% of dispersing agent (Dolapix CE64) by weight relative to the total weight is added to the crushed ferrite suspension (P2 ferrite particle suspension) in the previous step,

[0176] - the slip is ground for 7.5 hours with zirconium oxide beads yttrié of 0.1 mm diameter, with the following parameters:

[0177] - crusher speed: 14 m / s

[0178] - energy E2 between 6.2 and 7.1 kWh / kg

[0179] At the end of step S2, P3 ferrite particles are obtained.

[0180] The P2 and P3 particles thus obtained are observed by Scanning Electron Microscopy (SEM) using the FEI Quanta FEG 650 equipment in Large Field Detector Low Vacuum mode, with an accelerating voltage of 20kV, WD (Working Distance) 10mm, HFW (Horizontal Field Width) 5.60pm.

[0181] The size of the P3 particles is less than 200 nm, according to 20 dimensional measurements performed by image analysis. Due to the very small particle size, the measurements are indicative only to verify the consistency of particle size distribution measurements using the Laser Scattering Particle Size Distribution method.

[0182] Furthermore, the particle size and specific surface area measurements, carried out by the different techniques described above (laser diffraction analysis using the Laser Scattering Particle Size Distribution Analyser Malvem model Mastersizer 3000 according to the protocol described in the description and by the B ET (Brunauer, Emmett and Teller Method) with the "Micromeritics FlowSorb II 2300" equipment according to the protocol described in the description) and used for the characterization of the ferrite powders obtained according to the present invention, show that the P3 particles obtained in Example 2 by means of this two-stage high-energy grinding process have a specific surface area of ​​72 m2 / g and a diameter much less than 200 nm.

[0183] The particle size distribution of the P3 ferrite particles thus obtained is as follows: d90 = 117 nm; d50 = 78 nm and di0 = 50 nm. These results are consistent with the measurements obtained by SEM.

[0184] The particle size distribution of the P2 ferrite particles thus obtained is as follows: d90 = 1.149 pm; d50 = 0.465 pm and di0 = 0.196 pm. These results are consistent with the measurements obtained by SEM.

[0185] Pressing and sintering of ferrite particles after grinding

[0186] The P3 ferrite particles obtained above are shaped by uniaxial pressing into tori in the APC7 format. The shaped material is then densified by sintering at either 850 °C or 900 °C.

[0187] The microstructure of the sintered material at 900°C was observed by SEM-EBSD. The observation of grain sizes, i.e., the diameter of the equivalent sphere circumscribed by said particles, ds = VS / ji, where S is the surface area of ​​the equivalent sphere, was carried out by analysis of crystal orientation mapping. The observed equivalent diameters are less than 200 nm.

[0188] Table 3 shows the distribution of equivalent diameters of each grain size category observed by SEM-EBSD:

[0189] [Tables3] Surf, (pm2) Approx. Fraction (%) Grain Size "VS / n: ( nm) 0.005 23 40 0.015 20 69 0.025 17 89 0.035 11 106 0.045 9 120 0.055 6 132 0.065 3 144 0.075 3 155 0.085 1 164 0.095 2 174 0.105 2 183 0.115 1 191

[0190] The magnetic permeability of the materials thus obtained is characterized between 1 and 500 MHz using a Keysight model E4991B impedance meter according to the protocol described in the description. Figure 1 shows the permeability value and the value of αrùbj as a function of frequency for each of the two materials sintered at 850 °C and 900 °C. as well as for material which has followed a classic ceramic manufacturing process and has been sintered at three different sintering temperatures (1180, 1140 and 1100 °C).

[0191] Figure 1 shows the actual value of the permeability p' and tan(φ) (denoted "tanφ") as a function of frequency for the two materials obtained according to the invention ("high-energy process") sintered at 850 °C and 900 °C. Between these two temperatures, the performance of the materials changes. If a loss threshold tan(φ) is set at 0.1, the process according to the invention allows the material sintered at 850 °C to be used up to approximately 250 MHz with a p-value between 13 and 16 (over the range 1–250 MHz) compared to 160 MHz with a p-value between 21 and 25 (over the range 1–160 MHz) for the material sintered at 900 °C.

[0192] It is therefore observed that the performance of the materials obtained according to the process of the invention ("high-energy process") changes between the two sintering temperatures. For a loss threshold tan(ôjj) set at 0.1 (low magnetic losses), the process according to the invention allows for the following use:

[0193] - of sintered material at 850 °C up to about 250 MHz with a pr between 13 and 16 (over the 1-250 MHz range), and

[0194] - of the sintered material at 900 °C up to about 160 MHz with a pr between 21 and 25 (over the range 1 - 160 MHz).

[0195] In contrast, for the material obtained in Example 1 by a comparative process (“low-energy process”), it is observed that changing the sintering temperature does not have a significant impact on the frequency loss threshold. Indeed, regardless of the sintering temperature (1180, 1140, or 1100 °C), if a loss threshold tan(φ) is set at 0.1 (low magnetic losses), the maximum operating frequency of the material remains unchanged at 15 MHz in all three cases. It should be noted that materials not obtained by the process according to the invention cannot be sintered at a lower temperature because their densification is insufficient. Such a material is therefore unusable in the VHF and UHF frequency range, unlike the material produced by the process according to the invention which can be used up to frequencies of 160 MHz (sintered at 900°C) or 250 MHz (sintered at 850°C).

[0196] The process according to the invention therefore advantageously extends the frequency range of use of ferrite materials, and in particular of NiaZnbCucCodMneFe2-ôO4 type materials as described above, and also adapts the characteristics of the material by modulating the sintering temperature.

[0197] Example 3: Grinding process according to the invention

[0198] The following raw materials are selected and weighed according to Table 4:

[0199] [Tables4] Raw materials Quantity (g) Fe2O3 1910.8 NiO 677.7 Co3O4 50.4 ZnO 361.2

[0200] Preparation of ferrite particles:

[0201] The protocol for preparing the ferrite particles is the same as that of Examples 1 and 2, except for the composition of raw materials which is that described in Table 4.

[0202] The PL ferrite particles obtained have a specific surface area typically between 2 m2 / g and 4 m2 / g, a diameter d90 of about 30 pm, and have the following composition: Nio.684Zno34COo.048Fei,92804.

[0203] Grinding of ferrite particles:

[0204] The PL ferrite particles obtained above are ground in two stages by an attrition mill under the reference DYNO MILL ECM AP 05 of the brand WAB Group.

[0205] First step S1':

[0206] - the PI ferrite particles are suspended in aqueous slip, typically at a ratio of approximately 1.6 kg / L of ferrite powder / deionized water,

[0207] - 2% by weight relative to the total weight of the dispersing agent slurry (Dolapix CE64) is added to the slip,

[0208] - the slip is ground for 5.5 hours with zirconium oxide beads yttrié of 0.3 mm diameter, with the following parameters:

[0209] - crusher speed: 12m / s

[0210] - energy Ei between 2.8 and 3.3 kWh / kg

[0211] At the end of step SI', the ferrite particles P2' are obtained.

[0212] Second stage S2':

[0213] - 1.7% of dispersing agent (Dolapix CE64) by weight relative to the total weight is added to the crushed ferrite suspension from the previous step,

[0214] - the slip is ground for 8 hours with yttria zirconium oxide beads 0.1 mm in diameter, with the following parameters:

[0215] - crusher speed: 14 m / s

[0216] - energy E2 between 6.3 and 7.9 kWh / kg

[0217] At the end of step S2', the ferrite particles P3' are obtained.

[0218] The particles thus obtained are observed by Scanning Electron Microscopy (SEM). Particle size and specific surface area measurements were carried out by the different techniques described above (laser diffraction analysis using the Laser Scattering Particle Size Distribution Analyser Malvern model Mastersizer 3000 according to the protocol described in the description and by the BET (Brunauer, Emmett and Teller Method) with the "Micromeritics FlowSorb II 2300" equipment according to the protocol described in the description).

[0219] Particle size measurements show that the P3' particles obtained by this two-stage high-energy grinding process, according to the invention, have a specific surface area of ​​91 m2 / g and a diameter of less than 150 nm (SEM analysis).

[0220] The particle size distribution of the P3' ferrite particles thus obtained is as follows: d90 = 106 nm; d50 = 68 nm and di0 = 40 nm.

[0221] The particle size distribution of the P2' ferrite particles thus obtained is as follows: d90 = 0.769 pm; d50 = 0.420 pm and di0 = 0.157 pm.

[0222] Pressing and sintering of ferrite particles after grinding

[0223] The P3' ferrite particle powder obtained above is shaped by uniaxial pressing into tori in the APC7 format. The shaped material is then densified by sintering at 820°C.

[0224] The magnetic permeability of the material thus obtained is characterized using a Keysight model E4991B impedance meter between 1 and 600 MHz according to the protocol described above. Figure 2 shows the permeability value and taihbj as a function of frequency for this material.

[0225] It can be seen that for a loss threshold tan(φ) set at 0.1, the process according to the invention allows the use of this material up to approximately 590 MHz with a pr between 5 and 8 (over the interval 1 - 590 MHz). Such a material is therefore usable in the VHF frequency range, and even beyond.

[0226] By varying the composition of a material manufactured according to the process of the invention, the frequency ranges in which it is usable can be increased. It is therefore possible to manufacture, using the process of the invention, materials that can operate in VHF and UHF frequency ranges.

Claims

Demands

1. A process for preparing a ferrite material, the process comprising the following steps: - a step Si of grinding ferrite particles Pi with grinding beads Bb to obtain ferrite particles P2, the diameter d90 of the ferrite particles P2 being less than the diameter d90 of the particles Pb, said step Si being carried out at an energy Ei greater than 1.5 kWh / kg, preferably greater than 2 kWh / kg, preferably greater than 2.5 kWh / kg, preferably greater than 3 kWh / kg, and - a step S2 of grinding the ferrite particles P2 with grinding beads B2 to obtain ferrite particles P3, the diameter d90 of the ferrite particles P3 being less than the diameter d90 of the particles P2, said step S2 being carried out at an energy E2 greater than 5 kWh / kg, preferably greater than 5.5 kWh / kg, preferably greater than 6 kWh / kg, and the diameter of the beads Bi being greater than the diameter of the balls B2.

2. A method according to claim 1, wherein the ferrite particles Pi comprise, preferably consisting of, iron oxide (Fe2O3) particles and one or more oxides selected from nickel oxide (NiO), cobalt oxide (CoO), zinc oxide (ZnO), manganese oxide (MnO) and copper oxide (CuO).

3. A method according to claim 1 or 2, wherein the Pi ferrite particles have a specific surface area of ​​at least 2 m2 / g, preferably of at least 2.5 m2 / g, preferably of at least 3 m2 / g.

4. A method according to any one of the preceding claims, wherein the diameter d90 of the Pi ferrite particles is less than 50 µm, preferably less than 40 µm, preferably less than or equal to 30 µm.

5. A method according to any one of the preceding claims, wherein the diameter d90 of the P2 ferrite particles is less than 1.5 qm, preferably less than 1.0 qm, preferably less than 0.8 qm.

6. A method according to any one of the preceding claims, wherein the diameter d90 of the P3 ferrite particles is less than 200 nm, preferably less than 150 nm, preferably less than 120

7. 11111. A method according to any one of the preceding claims, wherein the P3 ferrite particles have a specific surface area of ​​at least 20 m2 / g, preferably of at least 30 m2 / g, preferably of at least 40 m2 / g, preferably of at least 60 m2 / g, preferably of at least 70 m2 / g.

8. A method according to any one of the preceding claims, wherein the diameter of the balls Bi is from 0.3 mm to 1 mm, preferably from 0.3 mm to 0.8 mm, preferably from 0.3 mm to 0.6 mm.

9. A method according to any one of the preceding claims, wherein the diameter of the B2 balls is less than 0.3 mm, preferably less than 0.2 mm, preferably less than or equal to 0.1 mm.

10. A method according to any one of the preceding claims, wherein the Bi and B2 beads are zirconium oxide beads.

11. A method according to any one of the preceding claims, such that during the grinding step and / or steps Si and / or S2 the ferrite particles PI and / or P2 are in suspension, preferably in suspension in water.

12. A process according to claim 11, wherein the and / or suspensions further comprise a dispersing agent, preferably selected from polyelectrolyte polymers, more preferably carboxylic acids.

13. A process according to any one of the preceding claims, wherein the Pi ferrite particles are obtained by a calcination step of powdered oxides and / or carbonates, said calcination step being carried out preferably at a temperature from 800°C to 1100°C and preferably for a duration from 2h to 4h.

14. A method according to any one of the preceding claims, wherein step S2 is followed by a pressing step, preferably uniaxial pressing and / or isostatic pressing, of the ferrite particles P3, to obtain a ferrite material.

15. A method according to claim 14, wherein the pressing step is preceded by a step of coating or atomizing the P3 ferrite particles.

16. A process according to claim 14 or 15, wherein the particle pressing step P3 is followed by a sintering step, preferably at a holding temperature from 800°C to 1000°C, preferably from 800°C to 850°C.

17. A process according to any one of claims 14 to 16, wherein the resulting ferrite material has the following composition: NiaZnbCucCodMneFe2-ôO4 with: 2(a+b+c+d+e) + 3(2-ô) = 8 0.05 < b < 0.5 0 < c < 0.25 0.005 < d < 0.25 0 <e<0,l 0 < ô < 0,08.

18. Ferrite material obtained by the process according to claim 16, characterized in that it has a microstructure whose grain size is less than 200 nm, preferably less than 150 nm, preferably less than 120 nm, preferably less than 100 nm.

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