METHOD FOR HEAT TREATING AN OBJECT

Abstract

A method is provided in which a lower box comprising a base, walls that surround the base and an open side, and an upper box comprising a cover, walls that surround the cover and an open side are provided. One or more objects are arranged on the base of the lower box. The object(s) are covered with the upper box such that the open side of the upper is oriented towards the base of the box, the walls of the upper box are arranged on the base of the lower box and a gap is formed between the walls of the upper box and the walls of the lower box. A powder material is introduced into the gap in order to form an assembly having an interior. The powder material provides a mechanical obstacle to gas exchange between the interior and the environment. This assembly is then heat treated.

Claims

1. A method for heat treating an object, the method comprising the following: providing a lower box comprising a base, walls that surround the base, and an open side, providing an upper box comprising a cover, walls that surround the cover and an open side, arranging the one or more objects on the base of the lower box, covering the one or more objects with the upper box such that the open side of the upper box faces the base of the lower box, the walls of the upper box are arranged on the base of the lower box and a gap is formed between the walls of the upper box and the walls of the lower box, introducing a powder material into the gap in order to form an assembly having an interior, the powder material providing a mechanical obstacle to gas exchange between the interior and the environment, and heat treating the assembly.

2. A method for heat treating an object, the method comprising the following: providing a plate, providing a box comprising a base, walls that surround the base and an open side, the base having at least one hole, arranging a powder material on the base of the lower box, arranging the plate on the powder material, arranging one or more objects on the plate, placing a cover on the box, the one or more objects thus being covered and an assembly having an interior being formed, the powder material providing a mechanical obstacle to gas exchange between the interior and the environment, and heat treating the assembly.

3. A method according to claim 1, wherein an inert material and/or a reactive material is used as the powder material.

4. A method according to claim 1, wherein the powder material comprises layers of different powder materials.

5. A method according to claim 4, wherein the powder material comprises a first layer containing an inert material and a second layer containing a reactive material.

6. A method according to claim 3, wherein the inert material is an oxide and/or the reactive material is an oxygen getter.

7. A method according to claim 3, wherein the reactive material is activated carbon or a metal powder.

8. A method according to claim 3, wherein the powder material comprises a content of at least one of the elements from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu of at least 15 wt %.

9. A method according to claim 1, wherein the base, the walls and the seams between the base and the walls of the lower box are gas-tight and wherein the cover, the walls and the seams between the cover and the walls of the upper box are gas-tight.

10. A method according to claim 1, wherein the gap filled with the material is covered by a frame and/or a cover.

11. A method according to claim 1, wherein the assembly is subjected to heat treatment at a temperature above 900° C.

12. A method according to claim 1, wherein the upper and lower boxes are made of molybdenum, an alloyed high-temperature steel or iron.

13. A method according to claim 2, wherein the plate and the box are made of molybdenum, an alloyed high-temperature steel or iron.

14. A method according to claim 2, wherein the assembly further comprises a support structure for the objects and the objects are arranged in the support structure.

15. A method according to claim 14, wherein the support structure comprises a plurality of plates that are stacked one on top of the other and held spaced apart by supporting frames, or the support structure has the form of a corrugated sheet.

16. A method according to claim 1, wherein the powder material comprises at least one element that is contained in the object in order to compensate for the evaporation of this same element from the object and/or to increase the vapor pressure of the element in the interior of the assembly.

17. A method according to claim 16, wherein the element is the rare-earth element samarium or dysprosium.

18. A method according to claim 16, wherein the object comprises a precursor having 2R and 17M, R being at least one of the elements from the group consisting of Ce, La, Nd, Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yt, Lu and Y, and M being at least one of the elements from the group consisting of Co, Fe, Cu and Zr.

19. A method according to claim 16, wherein the object comprises a Sm.sub.2Co.sub.17-based alloy that may comprise one or more of the elements from the group consisting of Ce, La, Nd, Pr, Gd, Tb, Dy, Ho, Er, Tm, Yt, Lu and Y in addition to Sm, and one or more of the elements from the group consisting of Fe, Cu, Zr, Ni, Hf and Ti in addition to Co, where 0 wt %≤Hf≤3 wt %, 0 wt %≤Ti≤3 wt %, and 0 wt %≤Ni≤10 wt %.

20. A method according to claim 1, wherein the object comprises La.sub.1-aR.sub.a(Fe.sub.1-x-yT.sub.yM.sub.x).sub.13H.sub.zC.sub.b, M being Si and optionally Al, T being one or more of the elements from the group consisting of Mn, Co, Ni, Ti, V and Cr, and R being one or more of the elements from the group consisting of Ce, Nd, Y and Pr, where 0≤a≤0.5, 0.05≤x≤0.2, 0.003≤y≤0.2, 0≤z≤3 and 0≤b≤1.5.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Various embodiments are explained in greater detail below with reference to the drawings.

[0047] FIG. 1A shows a cross section through an assembly for the heat treatment of an object containing at least one rare-earth element with a high vapor pressure.

[0048] FIG. 1B shows a plan view of the assembly from FIG. 1A.

[0049] FIG. 2A shows a cross section through an assembly according to an embodiment.

[0050] FIG. 2B shows a cross section through an assembly according to an embodiment.

[0051] FIG. 2C shows a cross section through an assembly according to an embodiment.

[0052] FIG. 3 shows two cross sections through an assembly having a retaining structure according to an embodiment.

[0053] FIG. 4 shows a cross section through an assembly having a retaining structure according to an embodiment.

[0054] FIG. 5A shows a cross section through an assembly according to an embodiment, in which a plurality of plates made of a LaSiFe alloy is arranged.

[0055] FIG. 5B shows a cross section through a comparative assembly in which a plurality of plates made of a LaSiFe alloy is arranged.

[0056] FIG. 6 shows a cross section through an assembly having a retaining structure according to an embodiment.

DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS

[0057] FIG. 1A shows a cross section through, and FIG. 1B shows a plan view of, an assembly 10 for the heat treatment of at least one object 11. The assembly 10 has a lower box 12 comprising a base 13, walls 14 that surround the base 13, and an open side 15. The lower box 12 thus has the form of a trough that is surrounded on the underside and at the edges by the base 13 and the walls 14 respectively. The assembly 10 also has an upper box 16 comprising a cover 17 and walls 18 that surround the cover 17, thereby forming an open side 19 that is located opposite the cover 17.

[0058] The one or more objects 11 are arranged on the upper side 20 of the base 13 of the lower box 12. The one or more objects 11 are then covered with the upper box 16 such that the open side 19 of the upper box 16 faces the base 13 of the lower box 12, the walls 18 are arranged on the upper side 20 of the base 13 of the lower box 12 and the cover 17 of the upper box is arranged above the objects 11. The upper box thus serves as a hood to cover the objects 11. The walls 18 of the upper box 16 are arranged inside the walls 14 of the lower box 12. The objects 11 are thus arranged in a closed interior 21 that is surrounded at the lateral sides by the walls 18 of the upper box and closed on the upper side by the cover 17 of the upper box 16 and on the underside by the base 13 of the lower box 12.

[0059] A gap 22 is formed between the walls 18 of the upper box 16 and the walls 14 of the lower box 12. In particular, the ring-shaped gap 22 is formed between the outsides 24 of the walls 18 of the upper box 16 and the insides 25 of the walls 14 of the lower box 12.

[0060] A powder material 23 is arranged in the gap 22. The powder material 23 provides a mechanical obstacle to gas exchange between the interior 21 and the environment 26 outside the assembly 10. The powder material 23 is introduced into the gap 22. In some embodiments the upper box 16 is first placed on the base 13 of the lower box 14 and the powder material 23 is then introduced into the gap 22. The walls 14 of the lower box 12 serve to hold the powder material 23 inside the assembly 10 and also to arrange the powder material 23 between the interior 21 and the environment 26. Technically, this means that the air pathway between the interior 21 and the environment 26 is at least partially blocked by the powder material 23. The assembly 10 is heat treated in this set-up.

[0061] The mean grain size of the powder material can be selected in order to set the density of the powder and the filled fraction of the volume of the gap 22. The mean grain size may be less than 500 μm, for example.

[0062] In some embodiments the composition of the powder material 23 or a fraction of the powder material 23 is selected so as to provide an active function such as a getter, e.g. an oxygen getter, as well as the purely mechanical obstacle to gas exchange.

[0063] In some embodiments the powder material 23 has various different compositions or powders. For example, the powder material 23 may contain an active material as well as a fraction of an inert material. The active material may, for example, be an oxygen getter such as activated carbon, or a metal powder such as aluminium, magnesium or calcium. In some embodiments the grains of the active material and the grains of the inert material are mixed together in the gap 22. In some embodiments, however, the different materials are arranged in the gap 22 in layers.

[0064] In some embodiments the powder material 23 contains at least one rare-earth element that is also contained in the object 11 in order to compensate for the evaporation of this same rare-earth element from the object 11 and/or to increase the vapor pressure of this rare-earth element in the interior 21 of the assembly 10 in order to prevent at least part of the rare-earth element from evaporating from the objects 11.

[0065] In some embodiments the object 11 contains at least one rare-earth element with a high vapor pressure such as samarium or dysprosium. The object 11 may be made of a SmCo alloy in the form of either a green body made of a compressed SmCo alloy powder or a pre-sintered object that already contains a Sm.sub.2Co.sub.17-based alloy. In this embodiment the powder material 23 may contain samarium, which may be present in the form of a samarium hybrid, for example. The composition can be selected in order to provide the desired vapor pressure with this powder material at the temperatures to be used.

[0066] The fraction of the powder material 23 containing a rare-earth element may, for example, be at least 15 wt % in order to increase the vapor pressure of the rare-earth element in the interior 21 and/or to compensate for the evaporation of these same rare-earth elements from the objects 11.

[0067] The lower box 12 and the upper box 16 may be made of molybdenum sheets that are, for example, as thin as possible, for example with a wall thickness of no more than 1 mm. The seams between the walls 14 and the base 13 and between the walls 14 are preferably gas-tight and may be welded. The seams between the walls 18 and between the walls 18 and the cover 17 of the upper box 16 may also be welded and thus gas-tight such that gas exchange takes place via the powder material 23 only, thereby preventing the evaporation of the rare-earth element in the object 11 and the penetration of undesired elements from the environment 26 into the interior 21.

[0068] In a simple embodiment, the lower box 12 and the upper box 16 may be made of iron foil, two foil sheets being bent to form a trough or a hood.

[0069] FIGS. 2A to 2C disclose assemblies 10 according to further embodiments. In FIG. 2A, both the lower box 12 and the upper box 16 have oblique walls 14, 18 such that the open side 15 of the lower box 12 has a larger area than the base 13. Similarly, the open side 19 of the upper box 16 has a larger area than the cover 17. Consequently, the gap 22 formed between the walls 18 of the upper box 16 and the walls 14 of the lower box 12 is not of regular width, the upper open region of the gap 22 being larger than the lower region.

[0070] In the embodiment shown in FIG. 2B, the lower box 12 has walls 14 that extend obliquely outwards, while the walls 18 of the upper box 16 are arranged approximately perpendicular to the cover 17 of the upper box 16 and thus approximately perpendicular to the base 13 of the lower box 12. The gap 22 formed in this assembly is also larger on the open upper side than on the lower side adjacent to the boundary between the base 13 of the lower box 12 and the walls 18 of the upper box 16.

[0071] FIG. 2C shows an example of an arrangement in which the different materials are arranged in layers 29, 27 in the gap 22. The lower layer 29 contains a rare-earth element and the upper layer 27 contains an active material. This embodiment can be used to prevent materials such as oxygen or moisture, for example, from penetrating into the interior 21 from the environment 26. It is, therefore, advantageous for this active material to be arranged immediately adjacent to the boundary to the environment 26 and so in the upper layer 27. At the same time, the evaporation of rare-earth elements from the objects 11 is prevented by the lower layer 29 in the gap 22 containing the same rare-earth element as the objects 11 and being arranged at the boundary to the interior 21.

[0072] The assembly 10 may be used to heat treat one or more objects 11 simultaneously. To reduce the cost of the production process, a plurality of objects 11 is generally heat treated simultaneously. A retaining structure may be constructed in the interior 21 in order to arrange these objects 11 in the interior 21 of the assembly 10. FIGS. 3 and 4 each show an arrangement having a retaining structure 30, in or on which a plurality of objects 11 is arranged, and which is then covered by the upper box 16. The powder material 23 is introduced into the gap 22 and the assembly 10 is then heat treated.

[0073] FIG. 3 shows two cross sections through an assembly 10 having a retaining structure 30 according to an embodiment. The assembly 10 may be constructed on a base plate 31, which is then arranged on legs or furnace supports 32. The retaining structure 30 is arranged on the upper side 20 of the base 13 of the lower box 12.

[0074] The base plate 31 may be made of CFC (carbon fiber composite). The lower box 12, which can also be called a trough, and the upper box 16, which can also be called a hood, may be produced from sheets of molybdenum or alloyed high-temperature steel. The width B of the assembly may be less than the height H and length L of the assembly 10. This arrangement can be used to increase the cooling rate of the assembly 10.

[0075] The powder material 23 is introduced into the gap 22 that is formed between the outsides of the walls 18 of the upper box 16 and the insides of the walls 14 of the lower box 12.

[0076] In this embodiment the retaining structure 30 takes the form of a plurality of flat plates 35 that are stacked one on top of another and held spaced apart by a plurality of vertical supporting frames 36. A plurality of objects 11 is arranged on the plates 35 between adjacent supporting frames 36 such that the objects 11 are stacked in a plurality of layers inside the interiors 21.

[0077] Plates or sintering trays with a U- or V-shaped profile can be used for rounded green bodies.

[0078] FIG. 4 shows a cross section through an assembly 10 having a retaining structure 30 according to a further embodiment. In this embodiment the retaining structure 30 consists of a supporting plate 35 on which a corrugated sheet 37 is arranged to take a first layer of objects 11. An object 11 is arranged in each of the troughs in the corrugated sheets 37 so that the crests of the corrugations are arranged between two adjacent objects 11 in the layer. The corrugated sheet 37 can be produced by bending a metal sheet such as a molybdenum or iron sheet, for example. On this first layer of objects 11 lies a second corrugated sheet 37, on which a second layer of objects 11 is then placed. In this embodiment the trough 12 takes the form of an iron cannister that is open at the top.

[0079] In this arrangement the powder material 23 that is arranged in the gap 22 between the trough 12 and the hood 16 is covered by a covering frame 38 such that the covering frame 38 is arranged in the gap 22. Furthermore, the trough 12 is also closed by a cover 39. Here, the cover 39 is crimped to the lower part of the iron cannister once the gap 22 has been filled, giving a very stable set-up that can be transported easily. The hood 16 is encased in the trough 12 and the cover 39.

[0080] The assembly 10 and the retaining structure 30 according to one of the embodiments described here can be used to produce permanent NdFeB- and SmCo-based magnets and LaFeSi-based magnetocaloric moulded parts. These objects are advantageously produced using powder metallurgy methods. The starting alloys are first pulverised to fine powders with a mean particle size of preferably <20 μm and, where necessary, a plurality of such powders is mixed together to form a specific composition. These powders are then made into the desired forms by a variety of re-forming processes. This may be by means of pressing with or without a magnetic field, but the powders can also be replaced by organic binders and this mixture then processed further to form sinterable green bodies by extrusion, tape casting or similar methods. In addition to the metal powder particles, these green bodies may also contain organic components such as binders, lubricants and dispersing agents, etc. These green bodies then go on to be placed in more or less closed containers in vacuum sinter furnaces, where volatile components such as organic components or hydrogen contained in the starting powders are pumped off at temperatures below 1000° C. Lastly, the parts are sintered at approx. 1000 to 1200° C. in a vacuum, hydrogen or also in an inert atmosphere, depending on the alloy system, to produce the desired final density. The finished sintered parts are then generally subjected to various further tempering treatments at lower temperatures in order to create specific material properties.

[0081] The present invention prevents the green bodies from reacting with the air and absorbing impurities such as oxygen, nitrogen and water vapor during transport between the forming stage and the sintering furnace or during storage between these two process steps. Moreover, it can also prevent the organic components that are initially expelled at low temperatures in the sintering furnace and then deposited on cold parts of the sintering furnace from re-diffusing back onto the parts at high temperatures and causing undesired carbon contamination. In the graphite-insulated furnaces that are often preferred on cost grounds, it can prevent the methane that forms due to a reaction of the hydrogen contained in some alloys with the graphite elements from resulting in further carbon contamination of the sintered parts.

[0082] This provides sinter packaging that, firstly, permits the sintering furnace to be charged with air in the conventional manner without the green bodies made of alloys containing rare-earth elements absorbing significant quantities of oxygen and humidity. Secondly, the sinter packaging itself can also prevent the further absorption of contaminants such as oxygen, carbon and nitrogen during sinter treatment. In addition, the packaging may very largely prevent the losses of volatile rare-earth elements such as samarium and dysprosium owing to evaporation during sinter treatment at temperatures above 1000° C.

[0083] Together, all these measures result in an improvement in performance. Moreover, the improved sinter packaging obviates the need to acquire costly, fully encapsulated transport systems between the forming stage and the sintering furnace.

[0084] There are no major requirements here as to the fit between the two boxes 12, 16 as they are substantially sealed by the bulk powder 23. The powder may also be pressed into the gap 22 using a suitable tool in order to prevent cavities in the bulk getter 23. The getter powder 23 may also be bedded in with a suitable inert solvent, which can then be pumped out again before sintering. To prevent the getter powder 23 from being stirred up during transport, evacuation and gas treatment, the entire set-up may also be covered with a cover. A series of preferred embodiments are described below.

[0085] In a simple case the two boxes 12, 16 are each folded from a piece of iron foil with a thickness of 0.1 mm, for example. This technique, in which the foil is used only once, is suitable for packaging large blocks weighing in excess of 5 kg. Two foil boxes, which are open at the top and larger in periphery than the green body, are folded. The larger of the two boxes 12 is then placed over the green body 11, which is placed in a glove box filled with inert gas. The green body 11 together with the foil casing 12 is then rolled by 180° about its longitudinal axis such that it lies approximately centrally in the open foil casing, which is open at the top. The smaller foil casing 16 is then placed over the green body 11 from above and the gap 22 between the two casings 12, 16 is filled with the getter powder 23. In principle, the charge set-up can be transported to the sintering furnace in this state. Alternatively, however, the set-up can also be covered with a further foil casing in order to prevent any spillage of getter powder during further transport and to prevent the air on the upper side of the bulk getter from being stirred up excessively, and so prevent the accelerated diffusion of the oxygen.

[0086] Instead of the single-use iron foil, it is also possible to make the sinter boxes from a solid steel sheet by welding together sheets of approx. 3 mm thickness. High-temperature-resistant steels, in particular, such as austenitic steel 1.4841, for example, are suitable here. There should also be a peripheral gap of approx. 5 mm between the inner cover and the outer box, which is then filled with the getter powder. The advantage of a set-up of this type is that it can be used multiple times and the pot-shaped base simultaneously serves as a dimensionally stable support for the green bodies.

[0087] High-temperature-resistant steels also tend to distort at temperatures of 1000 to 1200° C. This means that the sinter boxes can only be reused under certain conditions. These sinter boxes, which are open on one side, may therefore preferably also be made of molybdenum.

[0088] The side walls of the sinter packaging can preferably be inclined towards one another such that the resulting gap for the getter powder is wider at the top than at the bottom. This makes it easier to introduce the getter powder and requires less getter powder to achieve the same fill level. The external dimensions selected for the inner box at the lower end of the gap are preferably almost as big as the internal dimensions of the outer box. This simplifies the positioning of the inner box, which practically centres itself. A wedge-shaped cross section of the gap has a further advantage. If the getter powder starts to shrink during the sinter treatment itself, the getter cake that forms is able to slip downwards partially and so prevent the formation of an unwanted gap between the getter and the box or sinter box during sintering.

[0089] Where requirements in terms of the purity of the handling and sintering atmosphere are particularly stringent, a plurality of sinter boxes can also be arranged one on top of another. A number of different types may also be combined. For example, SmCo green bodies that are particularly sensitive to samarium evaporation can be packed initially into an inner double box made of molybdenum and then into a more cost-effective, secondary packaging. Since the second, outer packaging is not in direct contact with the sintered parts, cost-effective, dimensionally stable materials such as graphite, for example, which would otherwise react with the sintered parts, can be used. It is, of course, necessary to ensure that the outer getter material does not react with the material of the outer packaging.

[0090] The inner sinter boxes may preferably be taller than the associated outer sinter boxes. This makes the removal of the inner box after sintering easier. Alternatively, eyes or lugs may also be attached to the inner sinter box and grasped with the aid of an appropriate tool in order to open the sinter box.

[0091] The inner or lower boxes with the powder material such as a getter, for example, in the gap can be covered with a further hood. This hood may be a simple thin iron foil sheet (single-use packaging), but may also be a more solid, reusable hood. This covering hood prevents the powder from being stirred up during transport and heat treatment and so helps to maintain the activity of the material. This cover need not be a fully closed hood. It may simply be a ring-shaped frame that covers the gap containing the powder.

[0092] The height of the powder introduced into the gap should preferably be at least 1 cm. If the bulk powder level is lower there is a risk that the getter will not work sufficiently effectively. The width of the gap filled with the powder should preferably be 2 to 10 mm on the upper side and 0 to 10 mm on the underside. A wedge-shaped gap with a width of 5 mm at the top and 0 mm at the bottom is particularly advantageous.

[0093] Before transporting the filled sintering container, nitrogen—the inert gas usually used when handling green bodies—may preferably be replaced by argon. For example, the container complete with the green body and powder can be evacuated in a lock and then flooded with argon. As argon is heavier than air, this further slows the diffusion of oxygen into the powder bed and the activity of the getter is better retained for the sinter treatment itself.

[0094] The powder introduced into the gap may be an inert material such as SiO.sub.2, Al.sub.2O.sub.3 or rare-earth oxides, for example. Where this is the case, the powder simply acts as a diffusion barrier to gas exchange. The powder may also preferably consist of activated carbon or fine metal powders such as Al, Mg, Zr, Ti or Ca, for example, as used in vacuum and pipe technology. In such cases, the powder acts as an active getter and binds impurities as they flow through it. The getter powder itself preferably has a rare-earth content of at least 15 wt % and a grain size of <500 μm. In principle, all rare-earth elements La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, including Y, are suitable.

[0095] The getter powder may preferably have a mean particle size of >50 μm. This reduces the sinter activity of the getter powder, and so reduces the risk of the two sinter boxes being sintered together by the getter powder and being impossible to separate from one another easily after the sinter treatment. The getter powder may preferably contain >50% and have a particle size of <10 μm. This percentage of fine material considerably increases the reactivity of the getter and so improves the getter effect. The particle size and composition of the getter powder may be set such that it sinters itself to a sealed porosity during the sinter treatment, slides down the oblique side wall shown in FIG. 2A and connects the two sinter boxes tightly to one another. The getter powders may preferably have the same composition as the parts to be sintered. This means that the coarse powders and mixtures available in the process can be used as they are with the pulverised fine powders. The filter dusts occurring during pulverisation of the fine powder can also be mixed into the getter powders. The getter powders may preferably be produced by pulverising defective sintered parts. It is, however, important that these defective parts be free of organic residues and not subject to excessive oxidisation. Getter powders may preferably be produced by pulverising getter powders already used in past sinter treatments. Pulverising creates fresh surfaces and so reactivates the getter powders.

[0096] Powders are preferably only reused as getter powders if the rare-earth-element content (SE) satisfies the following equation:

SE>15 wt %+sum(O+C+N)*10,

where O, C and N are the oxygen, carbon and nitrogen contents in wt %.

[0097] The getter powder may preferably consist of a mixture of two components with different rare-earth-element contents. For example, one component may contain an intermetallic phase such as Nd.sub.2Fe.sub.14B, Sm.sub.2Co.sub.17, Sm.sub.2Fe.sub.17, SmCo.sub.5 or (La,Ce)(Fe,Si).sub.13, for example, while the second component consists of rare-earth hybrids such as NdH.sub.2, DyH.sub.2, SmH.sub.2 or LaH.sub.2, for example. At the sintering temperatures used, the intermetallic phases continue to form a stable framework while the components richer in rare-earth elements provide a better getter effect owing to their greater reactivity.

[0098] Recycled getter powders that no longer satisfy this condition may preferably be sufficiently reactivated by the addition of a component rich in rare-earth elements.

[0099] FIG. 5A shows a cross section through an assembly 10 according to an embodiment in which a plurality of objects 11 in the form of plates made of a LaSiFe alloy are heat treated. The LaSiFe alloy plates are stacked one on top of another. This stack is located on a molybdenum plate 41 and separated from it by means of a Nd.sub.2O.sub.3 separating agent. This arrangement is placed in a lower box 12 and covered with an upper box 16. The gap 22 between the walls 14, 18 of the lower and upper boxes 12, 16 is filled with getter powder 23.

[0100] The LaSiFe alloy is magnetocalorically active. La.sub.1-aR.sub.a(Fe.sub.1-x-yT.sub.yM.sub.x).sub.13H.sub.zC.sub.b is one example of a magnetocalorically active phase with a NaZn.sub.13-type structure, where M is Si and optionally Al, T is one or more of the elements from the group consisting of Mn, Co, Ni, Ti, V and Cr, and R is one or more of the elements from the group consisting of Ce, Nd, Y and Pr, where 0≤a≤0.5, 0.05≤x≤0.2, 0.003≤y≤0.2, 0≤z≤3 and 0≤b≤1.5. The La.sub.1-aR.sub.a(Fe.sub.1-x-yT.sub.yM.sub.x).sub.13H.sub.zC.sub.b starting powder of which the plates are formed is used as the getter powder 23.

[0101] FIG. 5B shows a cross section through a comparative assembly 100 in which a plurality of stacked plates 40 made of the LaSiFe alloy is arranged on a molybdenum plate 41. The molybdenum plate 41 is separated from the plates made of the LaSiFe alloy by means of a CaO separating agent. Rather than gas-tight boxes, this comparative assembly 100 contains a base plate 101 and a covering plate 102, the covering plate 102 being held above the plates 40 by means of a frame 103. This frame 103 is surrounded by the getter powder 123. The La.sub.1-aR.sub.a(Fe.sub.1-x-yT.sub.yM.sub.x).sub.13H.sub.zC.sub.b starting powder is used as the getter powder 123.

[0102] FIGS. 5A and 5B also show the points in the stack from which samples were taken to measure the content of the elements carbon, oxygen and nitrogen.

[0103] The results for assembly 10 according to the invention as shown in FIG. 5A are summarised in Table 1.

TABLE-US-00001 TABLE 1 (figures in wt %) Probe # C O N 1 0.014 0.35 0.014 2 0.011 0.34 0.013 3 0.010 0.33 0.012 4 0.009 0.32 0.012 5 0.014 0.30 0.013 6 0.013 0.32 0.013 7 0.010 0.32 0.013 8 0.011 0.31 0.013 9 0.010 0.33 0.014 Mittelwert 0.011 0.32 0.013 indicates data missing or illegible when filed

[0104] These results show that for the plates heat treated in the assembly according to the invention there are no major differences between the edge parts, i.e. samples 1 and 9, and the parts from the centre, i.e. parts 4 and 5. These results show that this set-up can be used to achieve a uniform composition and so uniform magnetocaloric properties across the area of the heat treated plates.

[0105] By contrast, in the comparative assembly 100 shown in FIG. 5b the oxygen content measured in the sample from the edge of the stack is higher than that measured in the sample from the middle, see Table 2.

TABLE-US-00002 TABLE 2 (figures in wt %) Probe # C O N 0.018 0.25 0.034 0.030 0.55 0.028 1 0.023 0.54 0.026 2 0.024 0.51 0.027 3 0.037 ~1.1 0.018 indicates data missing or illegible when filed

[0106] This comparison shows that the gas-tight boxes together with the getter powder can be used successfully to prevent negative influences on the composition of the content of the assembly, i.e. the composition of the LaSiFe plates, caused by the external atmosphere in the furnace. Consequently, the assembly according to the invention can be used to improve the magnetocaloric properties of the plates.

[0107] FIG. 6 shows a cross section through an assembly 10 having a retaining structure 30 according to a further embodiment. In this embodiment, as in the embodiment shown in FIG. 3, the retaining structure 30 consists of supporting plates 35 and supporting frames 36. Here, the lowermost supporting plate 35 also performs the function of the trough 12 in the assembly shown in FIG. 1. Together with the cannister base 53, it forms the gap 22 for receiving the getter 23. Here, the cannister base 53 is connected to the cannister wall 51 and the cannister cover 52 in a gas-tight manner, e.g. by welding. Together, the cannister wall 51, the cannister cover 52 and the cannister base 53 form a cannister 50 that corresponds to the hood 16 in FIG. 1. The canister base 53 has a hole that permits gas exchange between the interior 21 and the exterior 26. The hole 54 in this embodiment corresponds to the opening 15 in the trough 15 in FIG. 1.

[0108] The gas exchange between the sintered parts 11 in the interior 21 and the exterior takes place through this hole 54, the gas having to flow through the getter 23 since the outer can 50 is closed in a gas-tight manner by welding, crimping or soldering, for example. In this embodiment at least the gas-tight connection of the cannister cover 52 to the cannister wall 51 must be carried after the cannister has been filled with the sintered parts.