Patent Application
20190228892
The present invention describes a process for enriching particle surface layer and coating particles. The present invention is in the field of Mechanical Engineering, Electrical Engineering, Chemical Engineering and Materials Engineering.
Different methods of producing materials called SMCs (Soft Magnetic Composites) are currently being studied, aiming at developing industrially viable and economically sustainable methodologies.
The SMC consists of a ferromagnetic powder composite coated with insulating material which, when combined with powder metallurgy techniques, is an alternative to steels for electromagnetic purposes of great technological interest, such as rotary machines, sensors and solenoids of fast switching, motors etc.
As each iron powder particle is coated with an insulating material, the electrical resistivity of the components (parts) produced with the coated particles is increased, decreasing the magnetic losses of the component by parasitic currents. The efficiency of the components manufactured in SMCs in relation to laminated electrical steels increases for medium and high frequency applications, wherein their total magnetic losses are more dependent on the loss by parasitic currents between particles of magnetic material (dynamic loss portion) than losses by hysteresis (static losses).
Other properties of interest of this type of material include three-dimensional isotropic ferromagnetic behavior, with the possibility of improvements in thermal characteristics, flexibility in the design of processing and assembly, contributing to cost reduction in scale production.
In addition to an extensive academic literature on the development of SMC alternatives, a number of patents have been filed with different processes for the production and processing of these materials, such as iron powders and their alloys coated with organic materials such as resins (US 2012/0229245 A1) or inorganic materials such as phosphates (U.S. Pat. No. 8,187,394 B2), boron compounds (US 2010/0224822 A1) and silicates (US 2013/0181802 A1). Patent JP 2008063642 cites the formation of films via vaporization.
The SMCs with organic coating on the ferromagnetic particles present low cost and simplicity in the production of the material in the form of finished components. However, this class of composites presents a great disadvantage that is the low processing temperature possible, which considerably increases its component of static losses. In addition, degradation of the organic coating is common, also weakening its component of dynamic losses over time. As for the inorganic coatings, although usually more expensive, they expand the possibilities of processing, mainly in relation to temperature, allowing the reduction of the residual stresses and defects introduced in the compaction and, therefore, reducing the component of static losses. Nevertheless, even among the SMCs coated with inorganic materials found in the state of the art in scientific and patent literature, it is identified the need to develop strategies that increase the thermal resistance of the coating, allowing even higher processing temperatures, optimizing the loss properties of SMCs for a larger frequency band.
In the search for the state of the art, in scientific and patent literature, it was not found documents anticipating or suggesting the teachings of the present invention, so that the solution proposed herein has novelty and inventive activity in view of the state of the art.
The present invention comprises the production of soft magnetic composites (SMCs) of ferromagnetic particles coated by insulating phase, aiming at reducing their losses by parasitic currents and consequently increasing the efficiency of electrical machine components.
In a first object, the present invention presents a process for enriching the surface layer of ferromagnetic particles with alloying elements, aiming at the optimization of the subsequent coating step. This process is characterized by the enrichment of the surface layer of iron particles (or other metallic particles of magnetic material) with chemical elements that form stable compounds (oxides, nitrides, carbonitrides, hydrides and borides) such as manganese, silicon, aluminum, chromium, titanium, tantalum, vanadium etc. The enrichment can be accomplished by sublimation/resublimation, vaporization/condensation or even via interdiffusion by mechanical contact.
In a second object, the present invention comprises processes for coating the ferromagnetic particles, preferably the enriched ferromagnetic particles obtained by the first object, these being characterized by at least one of the subsequent steps:
(a) Coating the ferromagnetic particles (preferably those obtained by the process characterized in the first object) by mixing the powders by tumbling, such process being carried out by the addition of oxide materials and ferromagnetic particles to a drum containing steel spheres. The tumbling process has rotation and time controlled until the particles are coated by deposition of a very small particle size oxide material on the surface of a ferromagnetic particle larger than 50 μm. After the coating, it is carried out the compacting of the already coated powder and the sintering heat treatment of the components obtained in the compaction.
b) Coating the ferromagnetic particles (preferably those obtained by the process characterized in the first object) with boron compounds following the methodology of preparation of a solution of boric acid and isopropyl alcohol, and mixing that solution with the enriched ferromagnetic particles, promoting total wetting of the particles with this solution. After evaporation of the alcohol, the ferromagnetic particles coated with boric acid are obtained. Another way of obtaining this type of coating is to combine the ferromagnetic particles with a boriding mixture and, then, to apply a boriding thermochemical treatment. After the boriding thermochemical treatment, the ferromagnetic particles (now coated) are separated from the residues of the boriding mixture added prior to treatment. The coated ferromagnetic particles obtained through both processes are converted into parts components with the desired shape and size via compaction and sintering techniques.
c) Coating the ferromagnetic particles (preferably those obtained by the process characterized in the first object) with silicates and non-metallic submicrometric particles (for example, oxides, carbides, nitrides, fluorides etc.). This type of coating is obtained following the methodology of dispersion of non-metallic particles in an alkali metal silicate solution (sodium, potassium, among others or a mixture thereof) forming a glassy suspension of non-metallic particles; followed by wetting the ferromagnetic particles by said suspension of non-metallic particles; subsequent drying of the ferromagnetic particles wetted by the suspension of non-metallic particles, compaction and heat treatment.
These and other objects of the invention will be readily appreciated by those skilled in the art and by companies having interests in the art, and they will be described in sufficient detail for their reproduction in the following description.
In order to better define and clarify the content of the present patent application, the following figures are presented:
The following descriptions are given by way of example and not limiting the scope of the invention, and they will make the object of the present patent application more clearly understood.
In the case of the enrichment of the ferromagnetic particles with manganese, this can be done by mixing the ferromagnetic powder (with a particle size in the order of 80 to 400 μm) with fine powder of pure Mn or Ferromanganese of high Mn content, in the ratio of 1:0.1 to 2.
The mixture of ferromagnetic powder and manganese powder is placed in a refractory crucible (loose powder, that is, uncompacted powder) and said crucible is taken to the oven. The atmosphere for the heat treatment must be sealed, with internal pressure in the tube of about 0.2 to 0.4 atm, in order to favor the sublimation/deposition of the Mn on the iron particles. The atoms are incorporated in the surface of the iron particles due to the chemical potential gradient, either by mechanical contact between iron particles with the particles of Mn, or via the gas phase, since the Mn easily sublimates from the solid state (it has high sublimation vapor pressure). The difference lies in the fact that the enrichment occurs due to the chemical potential gradient of Mn between the treatment environment and the particles of iron. The desired enrichment should present the concentration profile as schematized in
In the present example, when it is desired to form an insulating film of Mn mixed oxide, after the enrichment treatment, the powder is cooled and a mixture of the enriched powder is prepared including up to 0.8% solid lubricant and from 0.1 to 3% of a reducible oxide in the form of a fine powder selected from iron oxide, nickel oxide, cobalt oxide or even copper oxide. The concentration profile is not affected by the compaction of the desired magnetic part, that is, the pressure applied in the compaction will not change the concentration profile. Thus, after compaction that should occur at pressures greater than 700 MPa, the presence of the Mn enriched layer will remain uniform throughout the surface of the particles.
Since the oxidation of the layer has as its driving force the concentration gradient of manganese, it will be much more uniform in its thickness, as well as, the control of its thickness will depend only on the concentration of manganese and the amount of oxygen available in the interior of the part, which depends on the amount of oxygen-rich phase used as an oxygen carrier.
After compaction molding, the parts are heat treated in a neutral or reactive atmosphere, at temperatures of about 500° C.
In another example, for the SMC materials generated from the enrichment of the particles with silicon, this occurs predominantly via mechanical contact between iron particles with the Si (or Si-rich) particles mixed together. However, the ‘driving force for enrichment is the same as previously described, that is, the chemical potential gradient.
To obtain these materials, ferromagnetic powder (having a particle size of the order of 80 to 400 μm) is mixed with fine Si or ferrosilicon powder with a content of greater than 20% by weight of Si (or other Si-carrying phase) in the ratio of 1:0.1 to 1:2.
The mixture of the ferromagnetic powder and the Si powder is placed in a refractory crucible (loose powder, that is, uncompacted powder) and said crucible is taken to the oven. The atmosphere for the heat treatment must be inert with inert gas flow, at this step, avoiding Si oxidation, which would prevent the diffusion and formation of the enriched layer.
In the present example, when it is desired to form an insulating film of Si mixed oxide, after the enrichment treatment, the powder is cooled and a mixture of the enriched powder is prepared containing up to 0.8% solid lubricant and from 0.5 to 3% of a reducible oxide powder selected from iron oxide, nickel oxide, cobalt oxide or copper oxide. The particle size of this oxygen-carrying oxide should preferably be about 10 to 100 times smaller than the particle size of the ferromagnetic powder used.
Subsequently, the compaction of the parts is carried out using, for example, a compaction pressure above 700 MPa so that the maximum porosity is eliminated.
After compaction, the parts are heat treated in a neutral or reactive atmosphere, at temperatures of about 500° C.
The present invention provides a process for coating ferromagnetic particles via dry powder mixing, using a cylindrical drum and steel spheres.
The ferromagnetic particles of interest have an average size ranging from 50 to 400 micrometers, depending on the application. Firstly, these particles pass through a spheroidization step in the cylindrical drum, wherein the steel spheres larger than 5 mm in diameter cause, as a function of the rotation of the drum, a mechanical conformation on the surface of the iron particles. This process promotes a change in the morphology of the particles, that is, the initial irregular surface of the particles becomes more rounded, or tend to spheroidicity.
After obtaining the spheroidized ferromagnetic particles, the oxide materials are incorporated into this same drum, and the coating process is performed.
The insulating oxide materials are embodied by soft iron, manganese, nickel, magnesium, silicon, aluminum, titanium, boron and ferrite oxides, each imparting a different feature in the coating of the ferromagnetic particles.
For the formation of the composites deriving from the mixture of iron particles and insulating oxides, oxides concentrations of 0.1 to 10% by volume, preferably by percentages of about 0.5 to 1% were used, wherein the oxides employed have size variations between 0.02 to 20 micrometers. Such a process is accomplished by the addition of oxide materials and ferromagnetic particles to the drum containing steel spheres. The tumbling process must occur until the particles are coated by deposition of the very small particle size oxide material on the surface of a much larger ferromagnetic particle.
Subsequently, the compacting of the parts is carried out, whose subsequent heat treatment is carried out in a neutral or reactive atmosphere, at temperatures of about 500° C.
By using ferromagnetic particles, preferably enriched and spheroidized (as described in paragraphs 32 and 44), the coating involving insulating oxides was performed from boron compounds, wherein boric acid (H3BO3) was used due to its characteristic of transformation into boron oxide and water at low temperatures. The manner of adding the boric acid was via liquid, through a solution containing boric acid and isopropyl alcohol. Said solution was prepared with the aid of a heating base with magnetic stirring, the concentration of boric acid in the solution can be from 1 g/L to 20 g/L and a ratio of powder mass per volume of solution of 2 g/L to 20 g/L can be used. The powder wetted with the solution is dried at room temperature and forced convection to increase the speed of the process.
The layer formed of boric acid on the surface of the iron particles depends, among other factors, on the acid content in the solution and also on the ratios between iron particle mass and the volume of the solution. Iron particles with different percentages of boric acid show differences in the layer. A mass percentage of boric acid between 0.05% and 1.0%, preferably between 0.1% and 0.5% may be used.
After the boric acid-containing powder was obtained, it is carried out a mixing with the solid lubricant, this being any compaction lubricant. The lubricant content may be between 0.1% and 1%, preferably between 0.3% and 0.5%. The function of the lubricant is to reduce the friction between the powder particles, thus avoiding the breakage of the boric acid layer, very high contents of lubricant tend to leave residual porosity after the heat treatment, reducing the magnetic permeability.
In the present invention, the compacting pressure may be between 700 MPa and 1000 MPa, preferably between 800 MPa and 900 MPa. In order to increase the final density of the composite, the compaction can be made warmly.
Finally, the compacted parts undergo a heat treatment in an inert or reactive atmosphere, at temperatures between 500° C. and 700° C. During this heat treatment, the boric acid added via liquid to the surface of the ferromagnetic particles passes through chemical reactions at temperatures between 150° C. and 200° C. The end product of these reactions is boron oxide and water vapor. Part of this generated vapor reacts with the surface of the ferromagnetic particles, finally obtaining an insulation formed of an iron oxide compound and boron.
The coating involving iron boride is produced in two steps, the first is the boriding thermochemical treatment and the second is the separation of the boriding mixture and the iron particle. 80% Fe and 20% boriding mixture, by mass, were mixed; the bonding mixture can be commercial mixtures, considering the ease of subsequent separation. The heat treatment can be done at a temperature between 900° C. to 1100° C., the holding time between 60 minutes to 240 minutes.
After the boriding thermochemical treatment, it is necessary the separation of the ferromagnetic powder with the boride layer and the compounds of the bonding mixture. The ferromagnetic powder with a layer of iron boride obtained should preferably contain the Fe2B phase, as shown in
The obtained bonded powder is then mixed with lubricant. The compacting pressure may be between 700 MPa and 1000 MPa, preferably between 800 MPa and 900 MPa. The heat treatment of the SMCs produced with the borided ferromagnetic powder may be carried out at temperatures between 500° C. and 1100° C., preferably between 700° C. and 900° C.
Table 1 shows the results of density, electrical resistivity and magnetic properties of SMCs developed with electrical insulation of boron compounds:
The execution of the process for coating the ferromagnetic particles, preferably spheroidized and enriched (as described in paragraphs 32 and 44), with glassy suspension of submicrometric particles (
1—Non-metallic particles (for example, Al2O3, TiO2, ZrO2, WC, B2O3) are dispersed in an aqueous solution of alkali metal silicate (for example, Na2O.nSiO2, K2O.mSiO2 or a mixture thereof);
2—A ferromagnetic base powder is immersed in this silicate dispersion; the spare liquid is removed, remaining the ferromagnetic powder soaked by the silicate dispersion;
3—The product is dried, leaving the ferromagnetic powder coated by a solid layer of alkali metal silicate with particles dispersed in the glassy phase.
The viscosity of the coating solution made in Step 1 increases with increasing concentrations of silicate and dispersed particles. Viscosity also increases with decreasing mean particle size. The higher the viscosity of said solution and its wettability in the ferromagnetic phase, the greater the thickness of the layer deposited on the base powder.
The higher the ionic radius of the alkali metal of the silicate (Fr>Cs>Rb>K>Na>Li), the greater the electrical resistivity of the silicate, allowing a lower thickness of insulation layer to be deposited on the particles to decrease the parasitic currents. In addition, various properties associated with alkaline ion movement of a mixture of different silicates (for example, (1-X)K2O.XNa2O.nSiO2) have large variations with orders of magnitude of difference compared to the isolated precursors. For example, a mixture of the form (1-X)Na2O.XK2O.4SiO2, with X about 0.5, exhibits a resistivity almost 10 times greater than a pure sodium or potassium silicate.
The smaller the submicrometric particles dispersed in Step 1, the greater their specific area, making their thermal absorption greater during the heat treatment. This also increases the viscosity of the glassy phase after it reaches the glass transition. These effects allow an increase in the heat treatment temperature without loss of the integrity of the coating.
To illustrate the effect of the suspended particles on the coating during the heat treatment,
Also during heat treatment, the particles dispersed in the silicate act as activators of the crystallization of the glassy phase, this effect being intensified for smaller particles. The crystalline phase of the silicates has a higher melting temperature than the temperature at which their amorphous form is fluidified. By adjusting the heating rate, temperature and holding time or by performing cooling and heating cycles, the use of the product produced by this invention can be processed at much higher temperatures than the simple use of pure glassy coatings.
For even higher temperatures, depending on the composition of the dispersed particles and the silicate used, they begin to dissolve in the glassy phase forming more viscous and resistive compounds during the heat treatment. For example, treated at a temperature above 800° C., alumina particles dispersed in sodium silicate dissolve forming sodium aluminosilicate. Thus, by adjusting parameters of the heat treatment cycle, such as heating rate, temperature and holding time, it is possible to optimize the properties for each object produced by the process described in this invention.
Iron particles having a mean diameter of 222 μm were dispersed in an aqueous solution of sodium silicate (11 mg/ml) with 11 mg/ml of particles of Al2O3 having a mean diameter of 20 nm dispersed. The spare solution is discarded and the particulate material is dried at 85° C. for 2 hours in a vacuum oven.
The product is mixed with 0.5% by weight of lubricant and compacted via uniaxial compaction at 800 MPa. The compacted green body is heat treated under inert atmosphere with a level at 400° C. for 30 minutes for extraction of the lubricant, and then a level at 600° C. for 30 minutes.
For the purpose of comparison, the same base iron powder having a mean size of 222 μm was coated only by the sodium silicate without the nanoparticle dispersion, compacted and heat treated under the same parameters cited in this example. The electrical resistivity value of this material was 1.28 μΩ·m, indicating that the dispersion of nanoparticles in the glassy phase increased the integrity and electrical resistivity of the material.
Table 2 shows the total loss value measured for an induction frequency of 60 Hz and maximum induction of 450 mT for materials produced as described in this example, with and without alumina nanoparticles, with final level of heat treatment at T=500° C. and 600° C.
The increase in heat treatment temperature from 500° C. to 600° C. causes the flow of sodium silicate without nanoparticles to the pores, as discussed above, allowing contact between the iron particles and increasing the total losses due to parasitic currents. This not only does not occur at 600° C. when using the process described in this invention, dispersing nanoparticles in the silicate, as at a higher temperature there is a greater relaxation of the residual stresses generated during compaction and exhibiting a decrease of 12% of total losses in relation to the sample treated at 500° C.
As an example of application of the SMCs materials presented in this invention, it is proposed the construction of an electric motor comprising stator tooth, pole shoe and stator crown.
The electric motor manufactured with the use of the material constituting iron particles and insulating presents some advantages in its constructive form, such as modularity and three-dimensional design.
The pole shoe located on the motor stator is embodied as comprising an optimized two- or three-dimensional shape for the magnetic flow lines, reducing iron losses and material volume while increasing motor performance, as shown in
The assembly process of the electric motor comprising an association between the stator crown segments, an association between the stator tooth and the stator crown segment, and an association between the pole shoe and the stator tooth, wherein the stator crown segment comprises a housing, for example, dovetail type, for association with the upper surface of the stator tooth, and wherein the pole shoe has a housing for association with the lower part of the stator tooth. Such an assembly allows the modularization of the motor, that is, the motor is composed of embedded parts and not of a single entire part.
A mixture (ratio 1:1) of spheroidized particles of pure iron and FeMn (with high Mn content) were conditioned in a refractory crucible and heat-treated in a resistive oven. The treatment temperature was 700° C., the oven atmosphere being inert and sealed. During this treatment the sublimation/deposition of the Mn on the iron particles occurred, wherein a percentage of manganese of about 12% could be quantified in the surface of the iron particles.
After the heat treatment step, it was necessary to carry out the separation of the enriched powder and the FeMn powder. As the average particle diameter of the two powders is distinct, 220 micrometers to the iron powder and 100 micrometers to the FeMn powder, a sieving can be performed to obtain the enriched iron powder.
Subsequently, the enriched iron powder was coated with boric acid (H3BO3) to promote the oxidation of the enriched surface during the heat treatment. This oxidation is caused by the release of water that occurs during the transformations of boric acid at low temperatures.
The manner of adding boric acid to the enriched iron powder was via liquid, through a solution containing boric acid and isopropyl alcohol. Said solution was prepared with the aid of a heating base with magnetic stirring, wherein the concentration of boric acid in the solution was 0.8 g/L and the mass percentage of boric acid in the enriched iron powder was 0.1%. The powder was wetted with this solution, and then dried at room temperature with forced convection to increase the speed of the process.
After the boric acid-containing powder was obtained, it was mixed with 0.3% solid lubricant. The compacting of the specimens was performed at a pressure of 800 MPa and, finally, the compacted parts underwent a heat treatment in an inert atmosphere, at a temperature of 500° C. for 30 minutes. During this heat treatment, the boric acid added via liquid to the surface of the ferromagnetic particles passes through chemical reactions at temperatures between 150° C. and 200° C. The end product of these reactions is boron oxide and water vapor, where part of that vapor reacts with the surface of the enriched iron particles thus forming a mixed oxide of iron and manganese.
Table 3 shows the results of density, electrical resistivity and magnetic properties of the SMCs developed with electrical insulation of mixed oxides of iron and manganese and boron oxide:
A mixture (ratio 1:1) of spheroidized particles of pure iron and FeMn (with high Mn content) were conditioned in a refractory crucible and heat-treated in a resistive oven. The treatment temperature was 700° C., the oven atmosphere being inert and sealed. During this treatment the sublimation/deposition of the Mn on the iron particles occurred, wherein a percentage of manganese of about 15% could be quantified in the surface of the iron particles.
After the heat treatment step, it was necessary to carry out the separation of the enriched powder and the FeMn powder. As the average particle diameter of the two powders is distinct, 220 micrometers to the iron powder and 100 micrometers to the FeMn powder, a sieving can be performed to obtain the enriched iron powder.
Subsequently, the powder was subjected to the coating process with non-metallic particles dispersed in alkali metal silicate, as described in item b) of the second object of the present invention and in more detail in paragraph 59, using sodium silicate and alumina nanoparticles (20 nm) for the coating suspension, both at a concentration of 1 mg/ml. The powder was dried at a temperature of 75° C. under vacuum forming a manganese-enriched iron composite coated by 0.02% by mass of sodium silicate with dispersed alumina nanoparticles.
The composite formed was mixed at 0.3% by mass of lubricant, compacted at a pressure of 800 MPa and, finally, treated under oxidizing atmosphere at 500° C. for 30 minutes. During this heat treatment the glassy composite of the coating, in addition to providing electrical insulation, releases water of crystallization of the silicate, oxidizing the surface of the enriched iron particles and forming a mixed oxide of iron and manganese, which provides an even greater electrical resistivity for the material.
Table 4 shows the results of density, electrical resistivity and magnetic properties of the SMCs developed with electrical insulation of mixed oxides of iron and manganese and sodium silicate with dispersion of alumina nanoparticles:
The examples shown herein are for the sole purpose of exemplifying one of the innumerable ways of carrying out the invention, but without limiting the scope thereof.
| Number | Date | Country | Kind |
|---|---|---|---|
| BR1020160196817 | Aug 2016 | BR | national |
| BR1020170182037 | Aug 2017 | BR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/BR2017/050245 | 8/25/2017 | WO | 00 |
