The present invention refers to the area of systems and processes for the production of permanent magnets, in particular nanostructured macroscopic or thin films having a high magnetic energy density for applications to high-efficiency electrical motors and generators.
The research on permanent magnets is the subject of generalized efforts on the global scale, enhanced by the need of producing miniaturized electronic devices, electrical current generators and dc motors.
The magnetic properties required for these materials can be summarized in a high coercivity and a high remanent magnetization, both implying a large area of the hysteresis loop proportional to the magnetic energy density, in turn defined as the product of the magnetic induction times the magnitude of the magnetic field (B×H), and usually measured in MGOe or in J/m3 (1 MGOe≈7742 J/m3). A permanent magnet with a high B×H product whose working point is at an intermediate position between coercivity and remanence (depending on shape and boundary conditions) is the source of very strong magnetic fields and is hardly influenced by any external magnetic field; therefore, it can induce strong electromotive forces and be an optimum choice for both motor applications and electrical generators. Usually, the most suitable materials contain alloys of rare earth metals and transition metals (Sm2Co17, SmCo5, Nd2Fe14B, Sm2 (CoFe)17, Sm2Fe17N3, etc.), where the first element's crystal structure brings about a high magneto-crystalline anisotropy (hard phase) while the transition metal contributes to the overall system's magnetic moment (soft phase).
In order to get cheaper high-performance permanent magnets, the content of rare earths is slightly reduced, preferably choosing an iron-neodymium alloy instead of a cobalt-samarium one, with the additional advantage of a better workability.
According to recent developments of the physics of magnetism, a specific mechanism, i.e. dipolar coupling, has been considered as a possible starting point for producing materials having very high energy product B×H (>1 MGOe) with a reduced rare earth metal concentration. These concepts have been described, for instance, in the work by Lee, Bauser, Higgins, Chen and Liu “Bulk anisotropic composite rare earth magnets”, J. Appl. Phys, 99, 08B516 (2006). Recent numerical simulations show that in principle the same performances could be achieved using nanostructured alloys containing less than 10% of stoichiometric rare earth-based compound; see for instance Skomsky and Coey “Giant energy product in nanostructured two-phase magnet”, Phys. Rev. B, 48, 21 (1993). According to these studies, the optimum structure to satisfy the requirements to get a good performance is represented by a lamellar nanostructured material, where the stoichiometric hard phase containing rare earth metals consists of a set of stacked layers with typical thickness of about ten nanometers, separated by other layers of a soft ferromagnetic material with thickness of about 100 nanometers. However, the available process techniques have not succeeded so far in fabricating macroscopic manufactures constituted of nanostructured multilayered composites on the industrial scale.
The main production methods for permanent magnets comprised of biphasic materials containing a rare-earth based, hard ferromagnetic phase and a soft ferromagnetic phase based on Fe, Co, Ni can be classified as powder metallurgy processes. In this case, uniaxial cold pressing is performed, followed by either sintering, or uniaxial hot pressing or isostatic hot pressing. As a consequence, the microcrystalline structure of biphasic alloys obtained in this way is not sufficient to reach the theoretical performances estimated in the literature. Such a major disadvantage is attributed to a loose control on the nanostructure of crystals obtained through these techniques and to the shape typically assumed by the inclusions of the rare-earth based alloys (which are spherical or cylindrical, i.e., definitely far from behaving as bona-fide lamellae).
The aim of the present invention is to obtain a process for manufacturing nanostructured, multilayered permanent magnets (both as thin films and macroscopic pieces) characterized by a high magnetic energy density, and allowing an excellently performing and inexpensive (because of the lesser content of rare earths) magnetic material to be obtained.
In view of reaching such aim, the present invention regards a process for producing permanent magnets of the type which implies depositing alloys as multilayered nanostructured material, such operation of depositing implying to deposit a first set of stacked layers of a hard ferromagnetic material, intercalating to said first set of stacked layers a second set of layers of soft magnetic material, which comprises providing said hard and/or soft ferromagnetic material as a solution of magnetic nanoparticles, bringing said solution of magnetic nanoparticles to means for spraying liquid micro-jets, spraying said solution to deposit said first set of layers and/or said second set of layers. The invention also regards a system for producing macroscopic permanent magnets, as well as a corresponding permanent magnet. According to a preferred characteristic of the invention, said means for spraying liquid micro-jets include printing inkjet heads. According to another preferred feature, includes using means for spraying liquid micro-jets including at least two nozzles and that the solution containing nanoparticles of a hard magnetic material is sent to one of the nozzles, the solution containing nanoparticles of a soft magnetic material being sent to the other nozzle.
By virtue of the above mentioned features, the process according to the invention presents the advantage of a complete control of the biphasic material at the multilayered nanostructure level, allowing the volume fraction of rare-earth based, hard alloys to be limited to the theoretically expected values. In addition, adopting micro-jet spraying allows the surface area of the produced magnet to be covered with a deposition detail of at least one tenth of a millimetre, if needed.
Additional features and advantages of the invention will result from the following description, with reference to the attached drawings given as mere non-limitative examples, where:
In brief, the production process according to the invention comprises a phase of production of either a thin film or a macroscopic body, nanostructured along a vertical axis by means of production elements including means for spraying liquid micro-jets, such as inkjet print systems. According to another feature of the invention, such a production phase is planned to be actuated in parallel by means of matrices of these production elements.
Inkjet printing technology, exceedingly versatile, and which is the same technology adopted in several home printers, is slowly being extended to a number of production areas, such as, for instance, the field of electronics and nanotechnologies, to arrive to digital printing of ceramic tiles.
Printers apt to produce plastic moulds in three dimensions are increasingly being used by architects, allowing to obtain in a short time the same result which previously required days of work; the same type of set-up will be shortly made available to retail customers, being able to produce bulk bodies of whatsoever kind by rapid prototyping. New inks are available and already being placed on the market; they are constituted of polymers able to carry an electrical current; insulating and semi-conducting polymers; polymers suitable as waveguides in photonics or as optical lenses; solutions containing metallic nanoparticles for fabricating micrometer-sized antennas, etc.
According to the present invention, it is envisaged to use such technology together with magnetic materials for permanent magnets, by using inks containing solute magnetic nanoparticles, possibly functionalised, to feed a print head preferably provided with two nozzles able to independently spray an ink, or solution, for the hard phase and an ink, or solution, for the soft phase. The print head sprays the solution on a substrate or on a growth surface. After evaporation of a solvent of the ink where nanoparticles are dissolved, the latter aggregate to form the continuous surface of a magnetic material. If the nanoparticle surface is functionalised with a suitable ligand, a specific bonding between nanoparticles having different nature becomes possible: for instance, coating a Nd2Fe14B nanoparticle with a first ligand (a-type) and a Fe nanoparticle with a second ligand (b-type), as it will be clarified in the following with reference to
The ligands are planned to be selected in order to determine a bonding energy such as to mechanically sustain the nanostructure even on a macroscopic scale, with a cohesive force larger of that of a compacted powder (so called “crude” or “green”).
An exemplary embodiment of the process according to the invention is now described with reference to
In
In the second step (hard phase deposition), shown in
Hard-phase magnetic nanoparticles 12 have, in this example, a diameter of about 10 nm and are functionalised by a second ligand b. The high magnetic anisotropy typical of hard-phase magnetic nanoparticles guarantees that they behave ferromagnetically at room temperature and up to at least 100° C.
As it can be observed, substrate 11 turns out to be coated by a layer 13 generated by the bonding of the first ligand a with the second ligand b. Therefore, hard-phase nanoparticles 12 give rise to a heterologous chemical bonding which takes place in layer 13, and their surface distribution will be determined by the shift of chemical equilibrium between ligand a fixed to substrate and ligand b present in the solution, which is bound to nanoparticles 12 on one side, and to the species ab generated by covalent bonding on the other side.
It is possible that the choice of size distribution of hard-phase nanoparticles 12 in solution will be made looking for a monodisperse system, i.e. a dispersion of particles having substantially homogeneous size, in order to optimise the homogeneity and smoothness of the layers.
Subsequently, as shown in
The choice of size distribution of soft-phase nanoparticles 14 will possibly involve a polydisperse system, in order to increase the coating density by effect of the presence of spheres able to fill the smallest interstices.
The above described deposition steps are repeated several times, to finally result in a sheet, or film, of nanostructured material 15, which can be observed in
Subsequently, the sheet of nanostructured multilayered material 15 is assembled in stack together with other sheets 15, after carefully removing their substrates through a detaching action of chemical nature (i.e., using a surfactant) or mechanical nature (i.e., using a blade); the stacks of sheets of nanostructured layers can be assembled as a tablet, a form typically exploited for the commercialisation of many permanent magnetic materials; generally speaking, the interface between any sheet of nanostructured material 15 and the adjacent one is not an obstacle for dipolar coupling, making similar to a super-lattice, from the viewpoint of magnetic properties, the macroscopic magnet produced through the process according to the invention.
Therefore, the sheets, or foils, of nanostructured multilayered material 15 are assembled in a stack in order to obtain a macroscopic body comprised of a stalk of sheets 15 with a total thickness, for instance, of the order of 1 cm. With 50 μm thick films, as previously pointed out, this amounts to using 200 sheets of nanostructured multilayered material 15. Such a macroscopically assembled body is then submitted to thermal treatment by hot uniaxial pressing in order to allow for: thermolysis of the carbonic phase 18 connecting each nanoparticle 12 or 14 to the respective ligand a or b; thermolysis of the same ligand; filling-up of porosity; and an increase of theoretical density.
A detail of the effects of thermolysis process id shown in
As mentioned, the described deposition process, according to a further feature of the invention, allows to use the printing heads in parallel in order to realize the deposition of the magnets elements. An illustrative diagram is shown in
In the example given by the circular regions 16 sheets for cylindrical permanent magnets are therefore originated. It must be noted that, in this regard, producing a permanent magnet with cylindrical shape, having 10 cm in height and 20 cm2 base surface, with a single printing head featuring point-to-point control approximately 0.8 millions transits are needed of printing head 30 over a specific circular region 16. Considering a mean deposition time, limited by the maximum control frequency of the piezoelectric nozzle, leading to 10 s per sheet, this corresponds to a total deposition time of 185 days. By using a parallel architecture as that shown in
According to a further aspect of the proposed process, it is allowed to gradually variate the composition of the nanostructured laminate, inserting a greater amount of hard phase nanoparticles, in particular a greater amount with respect to the standard composition adopted during the production with an additional layer used to increase the coercivity, either with one or more transits of the printing head or performing a deposition of the hard phase functionalized with the complimentary phase, for example, referring to the executive example given in
Therefore, the procedure and deposition system here described show multiple advantages over existing methodologies.
The procedure according to the invention appears advantageous with respect to the principal methodologies which are used for the production of permanent magnets with biphasic materials, constituted by a hard ferromagnetic phase containing rare earths and a soft ferromagnetic phase based on Fe, Co or Ni, classified as powder metallurgy processes, allowing to develop a microcrystalline structure of biphasic alloys allowing either to reach or approach the theoretical characteristics that have been indicated by literature papers.
A further advantage of the procedure, according to the invention, is given by the economy of precious rare earths, which in classical processes must be introduced in much more sized volumes in order to result in an effective interaction, either based on exchange or on dipolar coupling.
The procedure and systems according to the invention therefore allow advantageously a complete control over the multilayered nanostructured biphasic material that permits to realize different products featuring extremely high performances.
The use of means to spray liquid micro-jets such as those employed on board of inkjet printers allows a complete control over the bidimensional coverage of the area of the magnet in production; by controlling the two nozzles separately it is possible to spray the inks, or the solutions, corresponding to both hard and soft phases of the composite; the absolute chemical specificity of the ligands chosen to functionalize the nanoparticles allows to realize in practice the same ideal order chosen for the super-lattice.
Such precise control at the nanoscale of the procedure according to the invention allows to reduce up to theoretical values the volume fraction of rare-earth-based alloys.
Of course, without obtaining the principle of the invention, details of production and embodiments may be widely varied with regard to what is described and illustrated, without thereby departing from the scope of the invention. The process according to the invention is applicable to the production of extremely high energy product permanent magnets, for the fabrication of dc current motors with extremely high energy efficiency. For example an ideal application is the fabrication of household appliances, where very small energy consumption and high rotation speeds are required to satisfy the market demand, featuring stringent limits from the point of view of energy savings and sustainability. An alternative application is represented by dc motors for the automotive segment, characterized by a high specific power and reduced hindrance.
In a preferred embodiment, as described, the printing heads are equipped with at least two nozzles, and therefore with two corresponding micro-chambers used to pressurize some amounts of hard phase solution and soft phase solution respectively by means of the respective actuators either piezoelectric or thermal to spray the solution towards the external atmosphere, depending on the inkjet printing technology, well known per se. It is possible nevertheless to employ one single nozzle to spray both the hard phase magnetic nanoparticles solution and the soft phase solution, eventually disposing a cleaning cycle for the printing head.
Number | Date | Country | Kind |
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TO2008A000462 | Jun 2008 | IT | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/IB09/52502 | 6/11/2009 | WO | 00 | 12/13/2010 |