Patent Grant
11270840
The present invention relates to a process for producing magnets. In particular, the invention relates to a process for producing rare earth magnets.
Rare earth magnets, in particular permanent magnets of the NdFeB type (neodymium iron boron magnets), are known for their higher coercivity (resistance to demagnetisation) than conventional magnets. Such magnets have found application in a wide range of electrical components such as hard-disk drives (HDDs), electric motors (EMs) in electric and hybrid vehicles (EHVs) and in wind turbine generators (WTGs).
Fully dense or sintered NdFeB magnets are typically manufactured via a complex powder processing route from either cast NdFeB type alloys or by recycling sintered NdFeB magnets which are recovered from spent electronic devices. For example, in the well-established Hydrogen Decrepitation (HD) process, cast NdFeB alloys or recovered NdFeB magnets are reacted with hydrogen gas (typically at room temperature and 1-10 bar pressure) to decrepitate the bulk material into a friable powder. The cast alloys and recovered magnets consist of a Nd2Fe14B matrix phase and a Nd rich boundary phase. The Nd rich boundary phase reacts with the hydrogen first, forming NdH2.7 in an exothermic reaction. This exothermic reaction is sufficient to allow the Nd2Fe14B matrix phase to react with hydrogen forming an interstitial hydride solution of Nd2Fe14BHx (x≈3). This hydride formation results in a differential volume expansion (˜5%) of the crystal structure and the brittle structure fractures to form a friable powder.
The decrepitated powder is air sensitive (due to the presence of the hydride components) and it may react with moisture in the air, resulting in an undesirable increase in oxygen content and the formation of rare earth oxides and hydroxides (e.g. at triple points forming Nd2O3 and Nd(OH)3). The subsequent handling and manipulation of the friable decrepitated powder must therefore be conducted in an inert atmosphere. The use of additives such as dysprosium (Dy), which is in limited supply and thus expensive, may also be required to obtain high coercivities in the NdFeB magnets produced.
If necessary, the decrepitated powder can be reduced further to a finer powder by, for example, jet milling. Once milled, a magnetic field is applied to align the grains of the powdered material and thus achieve anisotropy. The material is then pressed and sintered at around 1000° C. to produce a magnet. In the case of recovered rare earth magnet material, it may be necessary to add small amounts of blending agents, such as NdH2, in order to give a certain amount of clean, metallic rare earth rich phase which is essential for sintering to full density.
Sintered rare earth magnets are brittle and are therefore extremely difficult to shape. For certain applications (e.g. high speed motors in, for example, the automotive sector) it is desirable to produce rare earth magnets in thin sheets which can be placed in layers with insulating sheets between, thereby increasing the performance of the magnets by reducing the eddy-current losses. Currently, the only way to manufacture such thin magnets is to slice the sheets from a solid sintered block. However, this process is very time consuming and results in a significant amount of the magnetic material being lost as waste.
In practice, in an attempt to overcome the difficulties in shaping brittle rare earth magnets, particles of melt-spun ribbon consisting of nanocrystalline grains of magnet material are often mixed with a binder to produce a range of bonded magnets.
However, these binders are non-ferromagnetic and hence result in a dilution of the magnetic strength. This effect can be reduced by employing anisotropic HDDR-based powder.
HDDR (Hydrogenation, Disproportionation, Desorption and Recombination) is a well-known process which is used to achieve grain refinement and alignment in powdered alloys such as NdFeB. The main aim of HDDR is to convert a coarser grained structure into a fine grain, highly coercive powder for use in the production of anisotropic polymer bonded magnets. The process typically involves heating NdFeB powder in H2 to high temperatures (generally around 750-900° C.), and then, whilst still at high temperatures, desorbing the H2 under carefully controlled conditions. During the hydrogenation and disproportionation stages, initially the Nd-rich grain boundary material reacts with the H2 to form a hydride, and subsequently the matrix grains of Nd2Fe14B disproportionate to form an intimate mixture of NdH2, Fe2B and α-Fe, according to the general reaction:
Nd2Fe14B+2H22NdH2+Fe2B+12Fe
When the pressure is subsequently reduced (e.g. by vacuum application) the hydrogen desorbs from the disproportionated material and the three constituents recombine to give grains of Nd2Fe14B but with a much reduced grain size. The grain size is typically reduced from approximately 5-500 microns in the starting material to approximately 300 nm in the HDDR material and this reduction results in a substantial improvement in the coercivity of the magnets.
The present invention seeks to provide an improved process for the production of rare earth magnets or to overcome or ameliorate at least one of the problems of the prior art processes, or to provide a useful alternative.
According to a first aspect of the present invention, there is provided a process for the production of rare earth magnets, the process comprising the steps of:
Surprisingly, it has been found that a disproportionated NdFeB alloy has improved ductility as compared to a powder produced by hydrogen decrepitation of the same material. Without being bound by theory, it is thought that the improved ductility of a disproportionated NdFeB may be related to the free iron constituent which is present in large quantities in the disproportionated material. An advantage arising from the improved ductility is that the alloy can be more readily mechanically processed and shaped without fracturing. The invention takes advantage of the increased ductility of the material in the intermediate disproportionated state by combining a HDDR process with mechanical processing of the material in the intermediate disproportionated state. The present invention thus provides a process which facilitates the production and shaping of rare earth magnets, and which may be particularly applicable to the production of thin magnetic sheets.
In some embodiments, the rare earth alloy is selected from NdFeB, SmCo5, Sm2(Co,Fe,Cu,Zr)17 and SrFe12O19. As is known by those skilled in the art, the transition metal content of Sm2(Co,Fe,Cu,Zr)17 is typically rich in cobalt but also contains other metals such as iron, copper and/or zinc.
In some embodiments, the rare earth alloy is NdFeB.
The rare earth alloy may be exposed to pure hydrogen gas, or it may be exposed to a mixture of hydrogen gas with one or more inert gases, for example nitrogen or argon. By “inert” it will be understood that the gas is non-reactive with the rare earth magnets under the conditions of use. In some embodiments, the rare earth alloy is exposed to an atmosphere comprising no more than 80% hydrogen, no more than 50% hydrogen or no more than 30% hydrogen. In some embodiments, the rare earth alloy is exposed to an atmosphere comprising at least 10% hydrogen, at least 40% hydrogen, at least 70% hydrogen or at least 90% hydrogen. The use of a non-explosive gas mixture simplifies the processing equipment and makes handling of the gas safer.
In some embodiments, the pressure (or partial pressure where a mixture of gases is used) of hydrogen gas is from 1 mbar to 20 bar, from 0.1 bar to 10 bar, from 0.5 bar to 5 bar, or from 1 bar to 3 bar. In some embodiments, the pressure (or partial pressure where a mixture of gases is used) of hydrogen gas is approximately 1 bar. Over a wide range of temperatures the equilibrium pressure for NdH2 is very low so that the disproportionation reaction can be achieved over a wide range of pressures and temperatures. The higher the pressure of hydrogen the faster is the disproportionation reaction.
In some embodiments, the hydrogen gas (or the mixture of gases if used) is introduced at a rate of from 10 to 20 mbar min−1.
The rare earth alloy is exposed to the hydrogen gas for a period of time which is necessary to effect disproportionation of the alloy. It will be appreciated that the period of time necessary to effect disproportionation will depend on factors including the batch size of the alloy, the hydrogen gas pressure and the temperature at which the method is carried out. In some embodiments, the alloy is exposed to the hydrogen gas for a period of time from 30 minutes to 48 hours, from 1 hour to 24 hours, from 1 hour to 12 hours, from 1 hour to 5 hours or from 2 hours to 4 hours.
Exposing a rare earth alloy to hydrogen in accordance with the method of the invention effects hydrogenation and disproportionation of the alloy. As is known by those skilled in the art, “disproportionation” is a reaction in which the alloy dissociates into at least two constituents which are different to the compound of the alloy, but which are formed from the same elements as the alloy.
For example, in embodiments wherein the rare earth alloy is NdFeB having a Nd2Fe14B matrix phase and a Nd rich boundary phase, the disproportionated alloy comprises the constituents neodymium hydride (NdH2), ferroboron (Fe2B) and predominantly iron (α-Fe). The disproportionated material has been found by the present inventors to have much improved ductility which is thought to be attributable to the free iron (α-Fe) constituent. This improved ductility enables the alloy to be more readily mechanically processed without external fracturing.
The formation of the disproportionated constituents can be observed by carrying out scanning or transmission electron microscope (SEM or TEM) studies on the disproportionated material.
The disproportionation may be complete or partial. When the disproportionation is complete, then none of the original alloy compound will be present, i.e. only the disproportionated constituents will be present. When the disproportionation is partial, then the original alloy compound will be present in addition to the at least two disproportionated constituents. Substantially incomplete disproportionation results in the presence of the brittle matrix phase, thus reducing the ductility.
In some embodiments, the rare earth alloy is exposed to hydrogen gas so as to effect complete disproportionation of the alloy.
The rare earth alloy used in the process may be a bulk solid (e.g. a cast ingot, solid sintered magnet, melt spun or strip cast flakes) or it may be a powder (e.g. powder resulting from the breakdown of melt spun ribbons, hydrogen decrepitated powder or recycled magnet powder). In some embodiments, the rare earth alloy is a bulk solid. The use of a bulk solid alloy is preferred since powdered rare earth materials are typically air-sensitive and typically require handling in an inert atmosphere. Provided that the hydrogen is introduced into the alloy at elevated temperature then the sample integrity can be maintained and external fracturing can be avoided.
Thus, an advantage of certain embodiments of the present invention is the production of aligned magnets via a non-powder route. Therefore, in comparison with some of the conventional manufacturing routes, some embodiments of the invention avoid the need for the careful handling of an air sensitive powder (e.g. under an inert atmosphere) while keeping the oxygen content of the resulting magnets to a comparatively lower level.
In some embodiments, the process further comprises casting a molten rare earth alloy into a mould and solidifying the alloy, prior to exposing the alloy to hydrogen gas. The alloy may be removed from the mould prior to exposing the alloy to hydrogen, or the alloy may remain in the mould during the hydrogenation and disproportionation step.
Surprisingly, the inventors have discovered that when a bulk solid rare earth alloy material is physically constrained (e.g. within a metal tube) whilst being exposed to hydrogen gas over a wide range of conditions, hydrogenation occurs without the alloy breaking apart into a powder.
Thus, in some embodiments, the rare earth alloy is constrained during the step of exposing the alloy to hydrogen gas so as to effect hydrogenation and disproportionation.
By “constrained” it will be understood that the rare earth alloy is at least partially confined within a constraining element. In some embodiments, the rare earth alloy is sealed within the constraining element. The constraining element may be, but is not limited to, a mould, a tube, a sleeve or a ring. The constraining element may be partly or entirely formed of metal, such as copper or stainless steel.
In some embodiments, the constraining element is formed of a ductile material. A “ductile material”, as used herein, is any metal or alloy which is capable of plastic deformation under ambient conditions (i.e standard temperature and pressure). An example of a suitable ductile material is copper. Constraining the alloy within a ductile material will facilitate the subsequent deformation process and result in the finished magnet having a thin coating of the material forming the constraining element. This provides both mechanical and corrosion stability.
The process may further comprise placing the rare earth alloy within a constraining element prior to exposing the alloy to hydrogen.
In some embodiments, the process comprises exposing a rare earth alloy to hydrogen gas at elevated temperature, wherein the rare earth alloy is constrained within a mould.
In some embodiments, the process comprises casting a molten rare earth alloy into a mould, solidifying the alloy and, while the cast alloy is within the mould, exposing the cast alloy to hydrogen gas.
In such embodiments, the cast alloy may be exposed to hydrogen gas soon after the casting step while the cast is still hot. This saves on the energy required to heat the cast alloy to an elevated temperature sufficient to effect hydrogenation and disproportionation.
In addition, the inventors have surprisingly found that a constrained rare earth alloy undergoes hydrogenation and disproportionation at lower temperatures when compared with the temperatures which are required to effect hydrogenation and disproportionation of an unconstrained alloy. Without being bound by theory, it is thought that local increases in temperature due to the constrained nature of the sample and the exothermicity of the hydrogenation and disproportionation reactions allow for a much lower reaction temperature than that anticipated from normal kinetic arguments. Thus, a further advantage of some embodiments of the present invention is that the hydrogenation and disproportionation may be carried out at a lower temperature than that of the prior art HDDR processes.
It will be appreciated that the elevated temperature at which the rare earth alloy is exposed to hydrogen must be sufficient to effect hydrogenation and disproportionation of the alloy.
In embodiments wherein the rare earth alloy is constrained, the elevated temperature is at least 400, at least 450, at least 500 or at least 550° C.
In some embodiments, the elevated temperature is at least 600, at least 650, at least 700, at least 750 or at least 800° C.
In some embodiments, the rare earth alloy is exposed to hydrogen gas at an elevated temperature of no more than 1000, no more than 900 or no more than 800° C.
In some embodiments wherein the rare earth alloy is constrained, the elevated temperature is no more than 700, no more than 600 or no more than 500° C.
It will be appreciated that the precise temperature employed will be additionally dependent on a number of factors including, for example, the alloy batch size and/or the composition of the alloy. With larger batches of the alloy the exothermic hydrogenation and disproportionation reactions may be larger and it is therefore anticipated that a lower temperature may be employed to initiate the disproportionation reaction.
In some embodiments, the process further comprises a step of homogenising the disproportionated alloy. Homogenisation is carried out under H2. In some embodiments, homogenisation is carried out at a temperature of at least 800° C. or at least 900° C., for example at around 950° C. Homogenisation may be carried out for at least 2 hours, at least 4 hours, at least 6 hours, at least 8, at least 10 or at least 12 hours. In some embodiments homogenisation is carried out for a period of from 1 to 12 hours, from 2 to 8 hours, or from 3 to 5 hours.
In some embodiments, the rare earth alloy is exposed to hydrogen gas at 1 bar at around 950° C. to effect disproportionation, and then the disproportionated material is homogenised at around 950° C. for about 6 hours.
Homogenisation may help to optimise the microstructure of the recombined alloy material, for example by reducing cavitation at stoichiometric composition. Inclusion of a homogenisation step is particularly advantageous when the rare earth alloy starting material is a cast alloy. To minimise the extent of the cavitation on recombining the multiphase alloy to produce a very fine grain with high coercivity, it is necessary to employ a very near stoichiometric (Nd2Fe14B) composition NdH2 or NdCu4Al4 may be added subsequently. This means that, in the fully homogenised state, the amount of intragranular Nd-rich phase is very limited or absent. However, because the alloy forms by a peritectic reaction, in the as-cast condition there will be significant levels of free iron together with corresponding regions of Nd-rich compositions. This is not the case for the rapidly cast alloy such as the melt-spun and/or strip cast alloy or those cast alloys containing small quantities of di-boride additions. In the case of a book-cast alloy, homogenisation treatment may help to reduce or eliminate the non-homogeneous free Fe and Nd-rich regions. The use of a stoichiometric composition also maximises the proportion of the permanent magnet component and eliminates cavitation.
Alternatively, cavitation may be reduced by applying a mechanical force to the alloy during the recombination process.
In some embodiments, the process comprises the steps of:
The process may further comprise the step of extracting the recombined alloy from the constraining element (e.g. the mould). In some embodiments, extraction from the constraining element may be carried out prior to or after degassing.
In some embodiments, mechanically processing the disproportionated alloy comprises pressing, rolling, compacting, shaping and/or extruding the disproportionated alloy. These processes can be carried out while the alloy is hot, or when it is cold. In some embodiments, the disproportionated alloy is hot pressed in a mould (for example, the mould in which the alloy was cast). Disproportionation also makes cold compaction of the powder easier.
In some embodiments, mechanically processing the disproportionated alloy comprises forming the alloy into sheets. In some embodiments, the sheets have a thickness of no greater than 2 cm, no greater than 1 cm, no greater than 0.5 cm or no greater than 0.1 cm. In some embodiments, the sheets have a thickness of at least 0.01 mm, at least 0.05 mm, at least 0.1 mm or at least 0.5 mm.
The process may further comprise forming (e.g. by punching, stamping or cutting) discrete pieces from a sheet of the rare earth alloy in order to provide individual magnets. The step of forming the discrete pieces from the sheet may be carried out before or after degassing.
Mechanical processing of a disproportionated cast alloy could induce texture in the material which, in turn, could produce a preferred crystallographic orientation of the grain and so help to form anisotropic magnets. In contrast, non-disproportionated materials cannot be mechanically processed because they are brittle.
It will be understood that during the degassing step of the process hydrogen is desorbed from at least one of the disproportionated constituents in the processed disproportionated material such that these constituents recombine to re-form the original alloy compound. For example, in embodiments wherein the alloy is NdFeB, the disproportionated material comprises NdH2, Fe2B and α-Fe which recombine to give NdFeB following hydrogen desorption. Disproportionated powder will be more compactible and can therefore be cold forged to form fully dense compacts prior to recombination.
Careful control of the degassing procedure can assist in the alignment of the grains during recombination and thus the production of anisotropic magnets with improved remanence (magnetic strength) and/or (BH)max values.
In some embodiments, the processed alloy is degassed at a temperature of no more than 1000, 900, 800, 700, 650, 600, 550, 500 or 450° C. In some embodiments, the processed disproportionated alloy is degassed at a temperature of at least 25, 50, 100, 150, 200, 250, 300, 350 or 400° C. In some embodiments, the processed disproportionated material is degassed at a temperature of from 200 to 900, 300 to 800, 350 to 850 or 400 to 800° C. In some embodiments, degassing is carried out at a temperature of from 600-700° C., e.g. about 650° C.
In some embodiments, the processed disproportionated alloy is degassed by the application of a vacuum. In some embodiments the processed alloy is degassed at a pressure of at least 6 mbar, at least 10 mbar, or at least 50 mbar. In some embodiments, the processed alloy is degassed at a pressure of no more than 1 bar, no more than 0.5 bar or no more than 100 mbar.
In some embodiments, the rate of pressure reduction is no more than 1 bar/min, no more than 0.5 bar/min, no more than 0.1 bar/min or no more than 0.05 bar/min. In some embodiments the rate of pressure reduction is at least 0.1 mbar/min, at least 0.5 mbar/min or at least 1 mbar/min.
In some embodiments, the processed alloy is degassed for a period of time from 30 minutes to 48 hours, 1 hour to 24 hours, 1 hour to 12 hours, 1 hour to 5 hours, 1 hour to 4 hours or 2 hours to 4 hours.
The recombined alloy may comprise grains of reduced size in comparison with the grains of the original alloy. Prior to disproportionation, the rare earth alloy may have a grain size ranging from 1 (min) to 500 μm (max), from 2 to 100 μm or from 5 to 50 μm. The recombined alloy (i.e. following degassing) may have a maximum grain size of less than 1 μm or less than 500 nm, for example approximately 300 nm. The reduced grain size leads to higher coercivity (resistance to demagnetisation), which in turn means that less of the expensive dysprosium (Dy) additive is required.
In some embodiments, the process further comprises a step of cooling the alloy. Cooling may be carried out prior to and/or during degassing and/or after degassing. In some embodiments wherein cooling is carried out after disproportionation and prior to degassing, cooling may be carried out in the presence of hydrogen. A hydrogen pressure of in the region of 0.3-0.8 bar (e.g. approximately 0.5 bar), may be used. This helps to maintain the material in the disproportionated state.
In comparison with conventional methods for producing fully dense sintered magnets, the process of the invention reduces the number of steps involved in the manufacturing process. This, in turn also reduces the production costs.
According to a second aspect of the present invention, there is provided a process for treating a rare earth alloy, the process comprising exposing a constrained rare earth alloy to hydrogen gas at elevated temperature so as to effect hydrogenation and disproportionation of the alloy.
It will be appreciated that embodiments described above in relation to the first aspect of the invention may apply equally to the second aspect of the invention as appropriate.
Embodiments of the invention will now be described by way of example only, with reference to the accompanying drawings in which:
The cast NdFeB type alloy is then reacted with hydrogen gas at room temperature to effect decrepitation of the alloy into a friable powder. Since the friable powder is air sensitive, the powder has to be stored and transported under an inert atmosphere (e.g. argon) and it is preferable to carry out all subsequent steps of the process in an inert atmosphere. The friable powder is then jet milled to reduce the size of the powder particles.
The particles of the milled powder are then aligned in a magnetic field and subsequently pressed to provide a green compact. Green compacts produced in this way will typically have a density of approximately 69% of the theoretical density of the finished magnet.
The pressed green compact is then sintered at a temperature of approximately 1000° C. The sintering process is required to further increase the density of the green compact and provide the fully dense NdFeB type magnet.
The disproportionated material is homogenised under hydrogen gas (1 bar) at ˜950° C. for up to 12 hours, such as 3-5 hours, to optimise the microstructure of the material.
The material is then mechanically processed by, for example, hot pressing or cold compaction to form a green compact. The green compacts produced in this way will typically have a density of approximately 94% of the theoretical density of the finished magnet.
In alternative embodiments, the disproportionated material could be extruded or hot rolled into thin sheets, followed by punching of the thin sheets to provide discrete pieces of material that will eventually form individual magnets.
Following hot pressing, the processed disproportionated material is degassed under vacuum at a temperature of around 650° C. to effect hydrogen desorption and recombination of the NdFeB type alloy. The resulting magnet can then be placed into a device, such as a motor.
With reference to
These processes results in the production of a fully dense aligned rare earth magnet without the need to produce an air-sensitive powder. Processes in according with the invention enable the production of rare earth magnets with a significant reduction in the number if process steps and materials wastage. The increased ductility of the intermediate disproportionated material allows the shaping of the alloy as desired.
The formation of the disproportionated constituents can be observed by carrying out SEM studies on the disproportionated material.
The ductility of the solid bulk disproportionated material obtained from hydrogenation and disproportionation of NdFeB was assessed by measuring the density of green compacts obtained by pressing the disproportionated material.
Powdered NdFeB was exposed to hydrogen at a rate of 10 mbar/min up to 1200 mbar, at a temperature of 875° C., and held for 1 hour to effect hydrogenation and disproportionation. SEM was used to determine that disproportionation was complete and that the NdFeB had fully converted to the constituents NdH2, Fe2B and α-Fe.
A uniaxial compacting pressure of 10 tonnes was applied to a 1 cm diameter die set containing the disproportionated material to form a green compact. The green compact formed from the solid bulk disproportionated material was found to have a density of 6.95 g/cc, and held its shape. The theoretical density of the final magnets produced is calculated to be 7.5 g/cc. Thus, the solid bulk disproportionated material was compacted to approximately 94% densification.
In contrast, upon pressing the brittle, friable Nd2Fe14BH3 powder obtained from hydrogen decrepitation of NdFeB, the green compact was found to have a density of 5.13 g/cc. Thus, the brittle, friable powder was compacted to approximately 69% densification.
In a further experiment, solid cast NdFeB was exposed to hydrogen at a rate of 10 mbar/min up to 980 mbar at 800° C. and held at temperature and pressure for 2 hours to effect solid hydrogenation and disproportionation. Again SEM was used to determine that disproportionation was complete and density was measured to be 6.87 g/cc.
A uniaxial compacting pressure of 20 tonnes was applied to a 2 cm diameter die set containing the solid disproportionated material. The compact formed from the solid disproportionated material was found to have a density of 7.26 g/cc and a height change from 0.41 cm to 0.13 cm. Thus, the solid disproportionated material was compacted to approximately 97% densification.
The much higher density of the disproportionated material compared to the decrepitated material and the large change in height of the solid disproportionated material indicates that the disproportionated material has a significantly improved ductility.
In this study, cast material of compositions Nd12.2Fe81.3B6.5 and Nd15Fe78B7 were employed. The materials were cut either into cylinders of ˜9.5 mm diameter and ˜5 mm in height, or cubes of ˜5×5×5 mm, using spark erosion, since this technique limits the chance of oxidation which could influence the disproportionation reaction.
Disproportionation Technique
To achieve disproportionation, the samples were heated under vacuum 915° C., and hydrogen was introduced to a pressure of 1200 mbar for varying periods of time of up to 6 hours. This technique avoids the hydrogen decrepitation process which occurs at lower temperatures, thus producing a completely solid material rather than a powder, and allowing compression, stress-strain measurements to be undertaken. The conditions were also adjusted to avoid formation of the more reactive NdH2.7 component, by cooling rapidly to room temperature under vacuum then heating to 350° C. with a 30-minute hold to remove H2. After a period of time sufficient to achieve 100% disproportionation (approximately 5 hours), the material was then cooled in hydrogen (1200 mbar) in order to maintain the disproportionated state.
Compression Trials
In order to assess whether there had been any radical change in mechanical behaviour resulting from disproportionation, both treated and untreated samples were compressed in 10 mm diameter specac die sets with an Atlas T25 press capable of a load of up to 20 tonnes.
Microscopy
A Joel 6060 and Joel 7000 scanning electron microscopes were employed in backscattered mode using 20 kV accelerating voltage in order to examine the structure of the disproportionated material both before and after deformation, in an attempt to relate the mechanical behaviour to any changes in the microstructure.
Magnetic Measurements
A Lakeshore vibrating sample magnetometer (VSM), capable of up to 1.5 T, was used to measure the magnetic properties of the material before and after compression.
Results and Discussion
The initial trials were carried out on the alloy Nd12.2Fe81.3B6.5 and specimens of this alloy were subject to a rapid compression test both in the initial condition and after the solid hydrogen disproportionation treatment by the method described above. The samples were compressed in a die set up to a maximum load of 15915 tonnes/m2. This provided a rapid means of assessing any effect of the hydrogen treatment on the mechanical behaviour prior to more detailed stress/strain measurements.
SEM Results
SEM analysis of the Nd12.2Fe81.3B6.5 starting material revealed three phases in the material; several large dark areas, several light spots and a large grey area. Because the composition of the alloy was near that of stoichiometry and the 2/14/1 phase (large grey areas) area formed by a peritectic reaction, then some dendrites of free Fe were seen together (dark areas). A possible unseen phase of NdFe4B4 may also be present in the material.
SEM analysis of the Nd15Fe77B8 starting material revealed that, unlike the Nd12.2Fe81.3B6.5 starting material, the material has no dark regions of Fe dendrites. Several larger areas of light Nd rich as well as a large area of the 2/14/1 phase were observed. Removing the Fe dendrites will considerably improve the magnetic properties of the recombined material.
After hydrogen treatment of the Nd12.2Fe81.3B6.5 material, the large majority phase of 2/14/1 had transformed into a much finer disproportionated structure. The dark regions of Fe dendrites remained as they will not react with hydrogen but have a coarser disproportionated structure surrounding them. The small bright areas of Nd rich still remain after treatment. As well as this a new phase has appeared, confirmed by EDX to be NdFe4B4. Under the conditions employed in these experiments, there was no evidence of any reaction of this phase with hydrogen.
The same hydrogen treatment was applied to the Nd15Fe77B8 material. The majority of the 2/14/1 material was transformed into the disproportionated phase, the lighter areas of Nd rich were still present and there was also a phase of NdFe4B4 material present along the Nd rich grain boundary which had become clearer after the formation of the disproportionated matrix.
Initial Compression Trials
Cylinders of NdFeB material were cut by a spark erosion technique to sizes of ˜9 mm diameter and varying heights from 4.1-5.4 mm (
The load was then increased to the maximum setting of 20 tonnes (˜3130 MPa). In the case of the treated samples, the compression dramatically changed the shape of the material which experienced a height change of up to 70%. The thin compacts could be handled without falling into a powder with little to no powder being left behind after the compression test (
These simple trials emphasise the dramatic change in mechanical behaviour after the hydrogen treatment with the untreated material exhibiting very little ductility. This dramatic change has been confirmed by the subsequent, more carefully controlled, compression trials.
It can be surmised that the highly ordered NdFe4B4 will be of a similar brittle nature to that of Nd2Fe14B. This was confirmed by further SEM analysis of a region of a treated Nd12.2Fe81.3B6.5 alloy after compression, as shown in
SEM analysis of a compressed sample revealed that where the disproportionated mixture had coarsened at the interface with the iron dendrites, it was possible to discern the elongated nature of the iron component such that the minor axis was perpendicular to the direction of compression (
The density of the s-HD material was determined by weighing the sample in air and then in diethyl phthalate. The untreated cast material exhibited a density 7.548 gcm−3. After disproportionation the density of the material was measured to be 7.154 gcm−3, and once compressed by 20 tonnes this value was measured to be 7.067 gcm−3. The maximum possible density of stoichiometric disproportionated Nd2Fe14B is 7.18 gcm−3 The difference between this value and the value measured is due to the Fe dendrites and NdFeB4 phases present in the book mould material.
Mechanical Testing
Cylinders (˜9 mm diameter and ˜5 mm height) of the disproportionated cast materials were compressed in order to ascertain the detailed stress-strain behaviour of the various samples.
Recombination Process
After the compression trials, some of the samples were recombined by heating under vacuum to 900° C. at a rate of 10° C./minute and then cooled rapidly to room temperature. This treatment produced a solid sample with no powder break off and this resulted in a slight rise in density to 7.278 gcm−3. This increase can be attributed to the transformation back to Nd2Fe14B. The formation of cavitation, as shown by SEM, will lower the overall density as will the extensive cracking of the NdFe4B4 phase. Another distinctive feature of the microstructure is the ragged interface with the Fe dendrites which is indicative of the partial homogenisation process.
Magnetic Measurements
In
The present investigations have demonstrated very clearly that the normally extremely brittle NdFeB-based alloys can be converted to a ductile form by the application of the solid disproportionation process. The present studies have shown that the intimate mixture of predominantly Fe and NdH2 exhibits substantial ductility and any brittleness originates from the presence of the NdFe4B4 which is fractured extensively after the compression treatment. Preliminary magnetic data has been obtained on the recombined material under present conditions has shown that it is possible to introduce anisotropy in the material through compression.
Thus embodiments of the process of the present invention may provide one or more of the following advantages:
| Number | Date | Country | Kind |
|---|---|---|---|
| 1511553 | Jul 2015 | GB | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/GB2016/052001 | 7/1/2016 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2017/001868 | 1/5/2017 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 20090032147 | Nozawa | Feb 2009 | A1 |
| 20120244030 | Maeda | Sep 2012 | A1 |
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| 103426623 | Dec 2013 | CN |
| 2016800383792 | May 2019 | CN |
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| Number | Date | Country | |
|---|---|---|---|
| 20180190428 A1 | Jul 2018 | US |
