Patent Grant
10229775
The present invention is related to a magnetocaloric cascade and to a method for fabricating a magnetocaloric cascade. It is further related to a magnetocaloric regenerator, a heat pump and a heat-pumping method involving the use of a magnetocaloric cascade.
Due to advances in materials research, the magnetocaloric effect (MCE) has emerged as an economically viable alternative to known fluid circulation cooling methods for industry and commercial applications even at room temperature, such as refrigerators, cooling systems for cryoproduction in the process industry, and air conditioning systems. Another field of application of the magnetocaloric effect is in thermomagnetic power generators, i.e., in the conversion of heat to electrical energy.
The magnetocaloric effect occurs under application of an external magnetic field to a suitable magnetocaloric material and under an ambient temperature in the vicinity of its Curie temperature. The applied external magnetic field causes an alignment of the randomly aligned magnetic moments of the magnetocaloric material and thus a magnetic phase transition, which can also be described as an induced increase of the Curie temperature of the material above the ambient temperature. This magnetic phase transition implies a loss in magnetic entropy and in an adiabatic process (thermal isolation from the ambient temperature) leads to an increase in the entropy contribution of the crystal lattice of the magnetocaloric material by phonon generation. As a result of applying the external magnetic field, therefore, a heating of the magnetocaloric material occurs.
In technical cooling applications, this additional heat is removed from the material by heat transfer to an ambient heat sink in the form or a heat transfer medium. Water is an example of a heat transfer medium used for heat removal from the magnetocaloric material. Subsequently removing the external magnetic field can be described as a decrease of the Curie temperature back below the ambient temperature, and thus allows the magnetic moments reverting back to a random arrangement. This causes an increase of the magnetic entropy and a reduction of the entropy contribution of the crystal lattice of the magnetocaloric material itself, and in adiabatic process conditions thus results in a cooling of the magnetocaloric material below the ambient temperature. The described process cycle including magnetization and demagnetization is typically performed periodically in device applications.
The described cooling effect can be increased by designing the magnetocaloric material as a sequence of layers with decreasing Curie temperatures, or, in other words, as a magnetocaloric cascade containing two or more magnetocaloric material layers in succession by descending Curie temperature. In such a magnetocaloric cascade, the first magnetocaloric material cools down the second magnetocaloric material to a temperature near the Curie temperature of the second magnetocaloric material, and so on with any further magnetocaloric material contained in the cascade. This way, the cooling effect achieved can be greatly increased in comparison with the use of a single magnetocaloric material.
US 2004/0093877 A1 discloses a magnetocaloric material exhibiting a magnetocaloric effect at or near room temperature and a magnetic refrigerator using such magnetocaloric material. Different compositions of the magnetocaloric material yield different magnetocaloric materials exhibiting different Curie temperatures, i.e., different temperatures of the magnetic phase transition. The magnetocaloric materials are arranged in a first and a second regenerator bed which are exposed to varying magnetic fields. The regenerators form the core of a magnetic refrigerator. Similarly, WO 2004/068512 A1 and WO 2003/012801 describe magnetocaloric materials having different Curie temperatures obtained from a material system of a certain composition by varying of individual constituents or the relative amounts of individual constituents.
US2011/0094243 describes heat exchanger beds composed of a cascade of at least three different magnetocaloric materials with different Curie temperatures which are arranged in succession by ascending or descending Curie temperature and are insulated from one another by intermediate thermal and/or electrical insulators, the difference in the Curie temperatures of adjacent magnetocaloric materials being 0.5 to 6 K.
U.S. Pat. No. 8,104,293 B2 discloses a magnetocaloric cooling device comprising a plurality of thermally coupled magnetocaloric elements, one or more reservoirs containing a fluid medium and two heat exchangers. The heat exchangers are thermally coupled to the magnetocaloric elements and to at least one of the reservoirs for transferring heat between the magnetocaloric elements and the environment through the fluid medium.
US 2011/0173993 A1 discloses a magnetocaloric element comprising at least two adjacent sets of magnetocaloric materials arranged according to an increasing Curie temperature. The magnetocaloric materials within a same set have a same Curie temperature. The magnetocaloric element further comprises initiating means for initiating a temperature gradient between two opposite hot and cold ends of the magnetocaloric element.
WO 2014/115057 A1 describes a magnetocaloric cascade containing at least three different magnetocaloric materials with different Curie temperatures, which are arranged in succession by descending Curie temperature, wherein none of the different magnetocaloric materials with different Curie temperatures has a higher layer performance Lp than the magnetocaloric material with the highest Curie temperature. At least one of the different magnetocaloric materials with different Curie temperatures has a lower layer performance Lp than the magnetocaloric material with the highest Curie temperature. The layer performance Lp of a particular magnetocaloric material layer is calculated according to formula: Lp=m*dTad,max with dTad,max: maximum adiabatic temperature change which the particular magnetocaloric material undergoes when it is magnetized from a low magnetic field to high magnetic field during magnetocaloric cycling, and m: mass of the particular magnetocaloric material contained in the magnetocaloric cascade.
According to a first aspect of the present invention, a magnetocaloric cascade containing a sequence of at least three magnetocaloric material layers having different Curie temperatures TC is provided, wherein
The parameter ΔS is a measure of an amount of isothermal magnetic entropy change that is achievable in a magnetic phase transition of the respective magnetocaloric material layer. The amount of isothermal magnetic entropy change can be determined by techniques known in the art, for instance by deduction from isothermal magnetization data or by deduction from isofield heat capacity data. It is a function of temperature. It may be quantified for instance in units of J/cm3/K or, more commonly, J/kg/K. For reasons of simplicity, even though an amount is meant in the present context, the parameter is not denoted herein by |ΔS|, but by ΔS The parameter ΔS quantifies a characteristic of a given magnetocaloric material layer and thus forms a parameter that is individually controllable layer per layer by proper design of the magnetocaloric cascade. A maximum amount ΔSmax of the isothermal magnetic entropy change is achievable at the Curie temperature TC of a given magnetocaloric material.
The parameter mΔSmax thus forms the absolute maximum of the entropy parameter mΔS as a function of temperature. It is a measure of an absolute maximum of the amount of isothermal magnetic entropy change that is achievable in a magnetic phase transition of the respective magnetocaloric material layer having a given mass m. For many magnetocaloric materials, the maximum amount of the isothermal magnetic entropy change is achievable at the Curie temperature TC of the given magnetocaloric material. The parameter mΔSmax is unambiguously defined for a given layer of a given mass and a given material composition due to a characteristic line shape of the temperature dependence of ΔS as a function of temperature. A magnetocaloric material therefore only has a single ΔSmax Typically, different magnetocaloric materials have different values of ΔSmax. Modifying the mass of a given layer can not only be used to adapt the crossing-point value of the entropy parameter mΔS with respect to a neighboring layer, but also to adapt the maximum mΔSmax.
The parameter ΔTC denotes a difference amount between Curie temperatures of a given layer and one next neighboring magnetocaloric material layer. Here, the respective Curie temperatures as measurable in absence of any applied magnetic field are meant. While the Curie temperature TC is a parameter that quantifies a characteristic of a given magnetocaloric layer, the parameter ΔTC describes a property of a given layer sequence of two layers, namely, a given layer and its next neighboring magnetocaloric layer of the cascade. As such, the parameter ΔTC reaches beyond a given individual layer. It relates to the design of the sequence of layers in the magnetocaloric cascade.
Regarding the definition of ΔTC, the following is noted: For reasons of simplicity, even though an amount is meant, the parameter is not denoted by |ΔTC|, but by ΔTC Furthermore, an ambiguity may be seen on first sight in the above definition of ΔTC. For an inner layer of the cascade, two different values of the parameter ΔTC could in principle be determined, because an inner layer has two next neighboring layers, one on each side. However, when comparing the parameter values of ΔTC within a cascade, no such ambiguity occurs because there is an order of determination of ΔTC along one of the two possible directions along the cascade. Suitably, the order of determination follows the direction of heat flow through the cascade, which depends on a given application case (cooling or heating). In any case, the set of values of ΔTC across a given cascade is identical irrespective of the order of determination. For the hot-side layer and the cold-side layer, of course, there is only one next neighboring layer because the hot-side layer and the cold-side layer form the outer layers of the cascade.
Maximizing the parameter mΔSmax/ΔTC at the hot-side layer or the cold-side layer of the cascade in comparison with the inner layer(s) of the cascade in embodiments further improves the performance of the cascade as a whole, as will be shown further below by way of examples. The achieved effect can also be described as a strengthening of the cascade at its respective outer end facing a hot side or a cold side of a heat pump.
The present invention thus recognizes the significance of the entropy parameter mΔSmax/ΔTC at the outer layer for improving the performance of the magnetocaloric cascade in pumping heat between a hot side and a cold side. The invention provides a performance improvement if only one of the hot-side and cold-side outer layers is improved by exhibiting a larger ratio mΔSmax/ΔTC than any of the inner layers, and even more so if both of the hot-side and cold-side outer layers is improved this way.
In the following, embodiments of the magnetocaloric cascade of the first aspect of the invention will be described.
An improvement is already achieved with a relatively small difference of mΔSmax/ΔTC in one of the hot side or cold-side outer layers in comparison with the inner layers. In preferred embodiments, the hot-side outer layer or the cold-side outer layer exhibits an amount of the ratio mΔSmax/ΔTC that is at least 1% larger in comparison with any of the inner layers. The use of “or” here is meant to include the case that the hot-side outer layer and the cold-side outer layer exhibits an amount of the ratio mΔSmax/ΔTC that is at least 1% larger in comparison with any of the inner layers as a further embodiment.
The advantageous effect of the present embodiment on the heat pumping capacity of the magnetocaloric cascade in comparison with known cascade designs becomes particularly strong towards higher temperature spans between the hot and cold sides of the cascade. This temperature span typically finds an at least approximate correspondence in the difference between the Curie temperatures of the hot-side outer layer and the cold-side outer layer. In comparison with prior-art designs for a given temperature span, such embodiments achieve heat pumping with improved performance also at a temperature difference between the Curie temperatures of the hot-side outer layer and the cold-side outer layer, which is larger than a nominal temperature span.
In three alternative embodiments of the magnetocaloric cascade, the strengthening measures described above with respect to the outer layers of the cascade concern a) the hot-side outer layer alone or b) the cold-side outer layer alone, or c) both the hot-side outer layer and the cold-side outer layer. Thus, when stating that the hot-side outer layer or the cold-side outer layer exhibits a larger ratio mΔSmax/ΔTC in comparison with any of the inner layers, the term “or” is to be understood as including all three mentioned alternatives.
Different measures for adapting the of the ratio of the maximum amount of the entropy parameter mΔS and the Curie temperature spacing, ΔTC, i.e., mΔSmax/ΔTC, can be used, either alone or in combination with each other, for accomplishing the design of suitable embodiments of the cascade.
One such measure implemented in some embodiments is increasing the amount of ΔSmax in comparison with any of the inner layers. A variation of ΔSmax can for instance be achieved by proper material choice, of course taking into account requirements of a given application case regarding the Curie temperature. Preferably, the hot-side outer layer or the cold-side outer layer exhibits an amount of the ratio mΔSmax/ΔTC that is at least 1% larger in comparison with any of the inner layers. In other embodiments, mΔSmax/ΔTC is larger by at least 5% at the hot-side outer layer or the cold-side outer layer than at any of the at least one inner layers. In another embodiment, the parameter mΔSmax/ΔTC is larger at the hot-side outer layer or the cold-side outer layer than at any of the at least one inner layers by at least 10%. In one embodiment, the hot-side outer layer or the cold-side outer layer exhibits an amount of the ratio mΔSmax/ΔTC that is at least 20% larger in comparison with any of the inner layers. In yet another embodiment, the hot-side outer layer or the cold-side outer layer exhibits an amount of the ratio ΔSmax/ΔTC that is no more than 150%, in other embodiments no more than 100% larger in comparison with any of the inner layers. The heat-pumping-power improvement increases almost in proportion with increasing the percentage by which the ratio mΔSmax/ΔTC is higher at the hot-side outer layer or the cold-side outer layer than at the inner layers. However, increasing the ratio by selecting a magnetocaloric material with a higher maximum ΔSmax of the entropy parameter requires attention to the line-width (FWHM) of the temperature dependence of ΔS of the selected material so as to achieve a high crossing-point value in combination with a given neighboring layer.
In accordance with another measure that can be used in the alternative or in combination with the mentioned measure, the hot-side outer layer or the cold-side outer layer exhibits a smaller amount of ΔTC in comparison with any of the inner layers. As is known per se, in material systems of magnetocaloric materials a variation of ΔTC can for instance be achieved by adaptation of stoichiometry, i.e., the different fractions of the constituent elements in the material composition within the given material system for designing a given layer of the cascade. In a further embodiment of the magnetocaloric cascade, the hot-side layer or the cold-side layer exhibits an amount of ΔTC that is at least 0.2% smaller in comparison with those any of the at least one inner layer. In another embodiment of the magnetocaloric cascade, the hot-side layer or the cold-side layer exhibits an amount of ΔTC that is at least 5% smaller in comparison with those any of the at least one inner layer. However, with regard to the lower end of preferred amounts of ΔTC, the hot-side layer or the cold-side layer preferably exhibits an amount of ΔTC that is no less than 0.25 K, preferably no less 0.5 K.
Another design parameter that is used in some embodiments to influence the crossing-point values of the entropy parameter ΔS is the line width of its temperature dependence, for instance the full width at half the maximum amount (ΔSmax), to be determined in units of K. To increase a large line width and thus increase the crossing-point value for a given pair of neighboring magnetocaloric layers, a mix of different magnetocaloric layers can be used in at least one of the layers. In some such embodiments, a sublayer sequence can be used, preferably one that does not reduce the maximum amount ΔSmax of the mix or sublayer sequence in comparison with a single layer.
The magnetocaloric cascade can be implemented with any suitable combination of magnetocaloric material layers. For each pair of next neighboring magnetocaloric material layers of the magnetocaloric cascade there exists a respective crossing temperature, at which an entropy parameter mΔS of both respective neighboring magnetocaloric material layers assumes the same crossing-point value, the entropy parameter mΔS being defined as a product of the mass m of the respective magnetocaloric material layer and an amount of its isothermal magnetic entropy change ΔS in a magnetic phase transition of the respective magnetocaloric material layer. In preferred embodiments, all crossing-point values of an entropy parameter mΔS of all pairs of next neighboring inner layers are equal, either exactly or within a margin of ±15%, to a mean value of all crossing-point values of all pairs of next neighboring inner layers of the magnetocaloric cascade.
The margin of variation of the crossing-point values of the entropy parameter mΔS of all pairs of next neighboring inner layers with respect to the mean value of all crossing-point values of all pairs of next neighboring inner layers of the magnetocaloric cascade is in some embodiments even smaller than ±15%. In some embodiments, the margin is ±10%, in others even only ±5%. The smaller the margin of variation, the higher tends to be the achieved improvement in the performance of the magnetocaloric cascade in pumping heat between a hot side and a cold side.
To achieve a high heat-pumping power in operation of the cascade, different magnetocaloric material layers of the cascade exhibit respective materials and respective masses which in combination provide the crossing-point values of the entropy parameter mΔS across the magnetocaloric cascade at no less than 60%, in some other embodiments no less than 70%, in further embodiments no less than 80% of a global maximum of the entropy parameter mΔS assumed in any of the magnetocaloric layers across the magnetocaloric cascade.
Due to different material properties, the temperature dependences of the entropy parameter exhibit line shapes that may differ considerably in their respective maximum amount mΔSmax and in their width, for instance to be determined as a full width at half maximum (FWHM) with respect to the maximum amount mΔSmax. A suitable choice of materials of the magnetocaloric cascade in this regard takes into account the Curie temperature spacing ΔTC between neighboring layers of the cascade. The smaller the Curie temperature spacing between two neighboring magnetocaloric layers of the cascade, the higher is typically the crossing-point value of the entropy parameter for these two layers. Furthermore, a width measure characterizing a function describing the temperature dependence of the entropy parameter mΔS forms a suitable parameter for influencing the amount of the crossing-point value of the entropy parameters of neighboring magnetocaloric materials in design of the cascade. For instance, for a given Curie-temperature spacing, increasing a full width at half maximum (FWHM) of the temperature dependence of the entropy parameter mΔS of at least one of two neighboring layers by suitable material selection typically increases the crossing-point value of the entropy parameter for two neighboring magnetocaloric materials in the cascade (assuming for simplicity of explanation that the maximum amount mΔSmax does not change). The Curie temperature spacing ΔTC and the FWHM may not only be determined by material selection from a given discrete set of materials. In some material systems, these parameters can be adapted quasi continuously by selecting a suitable composition of the magnetocaloric materials for the respective magnetocaloric layers. Several material systems covering different constituent elements in ranges of stoichiometries are known. Magnetocaloric material systems, from which materials for use in any of the embodiments of the magnetocaloric cascade can be selected in accordance with the respective requirements of the embodiments described herein, are for instance disclosed in WO 2014/115057A1, page 11, line 26, to page 14, line 31. The publication WO 2014/115057A1 as a whole is hereby incorporated by reference into the present specification. Example material systems are MnFePAs, MnAsSb, and MnFePSiGe. Such material systems offer a substantially continuous coverage of a range of Curie temperatures. A Curie temperature that is suitable for a particular magnetocaloric layer in a cascade design can be achieved by setting a proper stoichiometry of the constituent elements of the material within the material system. On the other hand, a broadening of the FWHM of the temperature dependence of the entropy parameter can for instance be achieved by mixing materials with slightly different stoichiometries into a single layer or by providing a magnetocaloric material layer with a sublayer structure, wherein the sublayers have slightly different stoichiometries, instead of a magnetocaloric layer of equal thickness and homogenous composition.
In some embodiments of the cascade of the present invention, magnetocaloric layers from different material systems are used in the cascade. These embodiments provide particularly high design flexibility for implementing the cascade design in accordance with the present invention. It is noted that magnetocaloric materials having a difference in their chemical constituents or stoichiometric composition are considered identical materials in the context of the present disclosure, provided that their material parameters relevant for implementing the magnetocaloric cascade in accordance with a given embodiment of the present invention assume identical values.
Typically, in many embodiments of the cascade of the present invention, neither the hot-side outer layer nor cold-side outer layer fulfils the crossing-point-value requirements that applies to the inner layers in accordance with the previously described embodiments. For clarity of reference, these embodiments will be referred to as the first group in the next paragraph. However, it is noted that in other embodiments of the cascade, it is not only the inner layers that exhibit this particular design with respect to the crossing-point values of the entropy parameter mΔS. In addition, (in a second group of embodiments) a cold-side outer layer pair formed by the cold-side outer layer and its next neighboring cold-side inner layer, or (in a third group of embodiments) a hot-side outer layer pair formed by the hot-side outer layer and its next neighboring hot-side inner layer also exhibit a crossing-point value of the entropy parameter mΔS that is equal, either exactly or within the margin of ±15%, to the mean value of all crossing-point values of all pairs of next neighboring inner layers of the magnetocaloric cascade.
According to a second aspect of the present invention, a magnetocaloric regenerator is provided that includes a magnetocaloric cascade according to the first aspect of the present invention or one of its embodiments.
The magnetocaloric regenerator shares the advantages of the magnetocaloric cascade of the first aspect of the invention.
The magnetocaloric regenerator can be implemented in many different embodiments. Some of these different embodiments comprise the magnetocaloric cascade of the first aspect in respective different shapes. In some embodiments, a plate shape is used. In other embodiments, the magnetocaloric cascade comprises one or more channels extending through the magnetocaloric cascade for accommodating a heat transfer fluid, or a plurality of microchannels. The magnetocaloric generator may comprise the magnetocaloric material layers in respective different material shapes. A magnetocaloric material layer is in some embodiments formed by a solid material layer or a porous material layer. In other embodiments it is formed by particles, which can be spherically-shaped, non-spherically shaped such as disk-shaped or irregularly-shaped compounds.
According to a third aspect of the present invention a heat pump comprising a magnetocaloric regenerator according to the second aspect of the invention or one of its embodiments is provided. The heat pump shares the advantages of the magnetocaloric regenerator of the second aspect of the invention.
In the following, embodiments of the heat pump will be described.
Embodiments of the heat pump are suitably configured to cyclically perform a pumping sequence including a temperature increase and a temperature decrease of the heat-pump working body.
The heat pump of further suitable embodiments further comprises a hot-side interface in thermal communication with the hot-side outer layer, a cold-side interface in thermal communication with the cold-side outer layer, and a heat transfer system, which is configured to provide a flow of a heat-transfer fluid between the hot-side interface and the cold side interface through the magnetocaloric cascade, wherein the Curie temperature of the hot-side outer layer is selected to be higher than a temperature of the hot-side interface in operation of the heat pump, or the Curie temperature of the cold-side outer layer is selected to be lower than a temperature of the cold-side interface in operation of the heat pump. In a cooling application, for example, the cold-side interface is configured to be in thermal contact with an object to be cooled, and the hot-side interface is configured to be in thermal contact with a heat sink.
According to a fourth aspect of the present invention, a method for fabricating a magnetocaloric cascade is provided. The method comprises
In one embodiment, all crossing-point values of an entropy parameter mΔS of all pairs of next neighboring inner layers are equal, either exactly or within a margin of ±15%, to a mean value of all crossing-point values of all pairs of next neighboring inner layers of the magnetocaloric cascade.
According to a fifth aspect of the invention, a heat-pumping method comprises
In the following, embodiments of the heat-pumping method will be described.
In one embodiment, the pumping sequence includes a temperature increase of the magnetocaloric cascade which is performed in thermal communication with a heat sink. The pumping sequence is performed using a magnetocaloric cascade with the hot-side outer layer being a magnetocaloric layer with a Curie temperature that is between 0.5 K and 5 K higher than a heat-sink temperature.
Further embodiments are disclosed in the enclosed claims.
In the following, further embodiments will be described with reference to the enclosed drawings. In the drawings:
The outer layers 32 and 42 of both embodiments are strengthened in these two embodiments of the present invention, as will be explained in the following. In the embodiment of
In the embodiment of
Both measures described achieve an improvement of heat-pumping performance.
In another embodiment similar to that of
In yet another embodiment similar to that of
In a further embodiment similar to that of
In the following, further embodiments of cascades will be discussed with reference to
Virtual experiments were carried out using a physical model similar to that described by Engelbrecht: “A Numerical Model of an Active Magnetic Regenerator Refrigeration System”, http://digital.library.wisc.edu/1793/7596). A one-dimensional model was employed. The magnetocaloric material layers of the cascade of all examples underlying the diagrams of
A cooling power was determined for a reference cascade that is not in accordance with present invention and used for comparison only. The reference cascade has the following properties. It comprises a sequence of seven magnetocaloric layers, exhibiting equally spaced Curie temperatures with 3 K spacing. Curie Temperatures (in units of ° C.) were the following: 15.7 (cold-side outer layer); 18.7; 21.7; 24.7; 27.7; 30.7; 33.7 (hot-side outer layer). The layers had the same reference mass of 0.025 kg per layer, and a pumped volume per blow of 2×10−6 m3.
The cooling power was determined for the reference cascade and for different embodiments of the cascades of the present invention as explained in the following examples 1 and 2.
A first embodiment is a magnetocaloric cascade, which also has a layer sequence of seven magnetocaloric layers and the same mass per layer as the reference cascade and thus the same overall mass of the cascade in comparison to the reference cascade. However, the materials of the next neighboring inner layers of the hot-side outer layer and of the cold-side outer layer are chosen to have a smaller amount of Curie temperature difference ΔTC to the hot-side and cold-side outer layer, respectively. For both the hot-side and the cold side outer layer, the Curie temperature difference ΔTC with respect to its next neighboring inner layer amounts to 2.6 K. All inner layers have a Curie temperature difference of 3.2 K to their respective next neighboring inner layer. The absolute values of the Curie Temperatures (in units of ° C.) of the magnetocaloric layers of the cascade are the following: 15.7 (cold-side outer layer); 18.3; 21.5; 24.7; 27.9; 31.1; 33.7 (hot-side outer layer). Only results for spans above 18 K, which is the overall span in Curie temperatures are relevant and presented in the following.
The same reference cascade as for Example 1 was used.
A second embodiment is a magnetocaloric cascade, which also has a layer sequence of seven magnetocaloric layers as the reference cascade. However, the cascade of the second embodiment has variations in the mass in comparison with the reference cascade, as will be described below. The overall mass of the cascade in comparison to the reference cascade is maintained the same. However, the hot-side outer layer and the cold-side outer layer have an identical mass that is higher than the mass of the individual inner layers of the cascade by 20%. Thus, the overall mass of the inner layers taken together is reduced by 20%. The inner layers have identical masses in comparison with each other.
Other than in the first embodiment, the materials of the next neighboring inner layers of the hot-side outer layer and of the cold-side outer layer are chosen to have the same Curie temperature difference ΔTC to the hot-side and cold-side outer layer, i.e., the same Curie temperature difference ΔTC to the hot-side and cold-side outer layer, respectively, as to the respective next neighboring inner layers, namely 3.0 K. The absolute values of the Curie Temperatures (in units of ° C.) of the magnetocaloric layers of the cascade are the following: 15.7 (cold-side outer layer); 18.7; 21.7; 24.7; 27.7; 30.7; 33.7 (hot-side outer layer).
The diagrams of
The results are similar for cascades where the two outer layers (or even more) at one or both sides are modified using a higher mass per layer or a smaller Curie temperature spacing).
A cooling power was determined for a second reference cascade that is not in accordance with present invention and used for comparison only. The reference cascade has the following properties. It comprises a sequence of seven magnetocaloric layers, exhibiting equally spaced Curie temperatures with 3 K spacing. Curie Temperatures (in units of ° C.) were the following: 15.7 (cold-side outer layer); 18.7; 21.7; 24.7; 27.7; 30.7; 33.7 (hot-side outer layer). The layers had the same reference mass of 0.025 kg per layer, and a pumped volume per blow of 2×10−6 m3. The flow rate can be optimized for a given application case by known means. The second reference cascade differs from the reference cascade described above in the context of the Example 1 in the material of the magnetocaloric layers of the cascade, thus giving rise to a different lineshape of ΔS as a function of temperature, and to a different ΔSmax. The material of all layers of the second reference is identical and has a ΔSmax of 8.85 J/kg/K.
The cooling power was determined for the reference cascade and for different embodiments of the cascades of the present invention as explained in the following examples 3 and 4.
The cascade of Example 3 differs from the reference cascade only in that the material of the hot-side outer layer and the cold-side outer layer has a different maximum isothermal magnetic entropy change ΔSmax than the material of the hot-side outer layer and the cold-side outer layer of the reference cascade. The amount of ΔSmax of the hot-side outer layer and the cold-side outer layer of the reference cascade is 10.97 J/kg/K.
The same second reference cascade as for Example 3 was used.
The cascade of Example 4 differs from the reference cascade in that the hot-side outer layer and the cold-side outer layer both have a mass that is different from the hot-side outer layer and the cold-side outer layer of the reference cascade. The mass is increased in comparison with the hot-side outer layer and the cold-side outer layer of the reference cascade by 20%. Furthermore, the mass of the inner layers is reduced in mutually identical amounts so as to maintain the same overall mass of the cascade of Example 4 as that of the second reference cascade.
The same second reference cascade as for Example 3 was used.
The cascade of Example 5 differs from the reference cascade in that the cold-side outer layer has a Curie temperature spacing to its next neighboring inner layer that is smaller than the corresponding Curie temperature spacing of the reference cascade. The other Curie temperatures across the cascade of Example 5 are increased in comparison with those of the reference cascade. The Curie temperature spacings in units of K across the cascade are as follows: 3.08 (hot side)/3.08/3.08/3.08/3.08/2.6 (cold side).
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2015/078848 | 12/7/2015 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2016/096509 | 6/23/2016 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 8104293 | Barve et al. | Jan 2012 | B2 |
| 20040093877 | Wada et al. | May 2004 | A1 |
| 20110094243 | Carroll et al. | Apr 2011 | A1 |
| 20110173993 | Muller et al. | Jul 2011 | A1 |
| 20120043497 | Katter | Feb 2012 | A1 |
| 20130019610 | Zimm | Jan 2013 | A1 |
| Number | Date | Country |
|---|---|---|
| 102516950 | Jun 2012 | CN |
| 2482884 | Feb 2012 | GB |
| WO 03012801 | Feb 2003 | WO |
| WO 2004068512 | Aug 2004 | WO |
| WO 2014115057 | Jul 2014 | WO |
| Entry |
|---|
| International Search Report dated Feb. 16, 2016 in PCT/EP2015/078848 filed Dec. 7, 2015. |
| Nguyen H. Dung, et al., “Mixed Magnetism for Refrigeration and Energy Conversion”, Advanced Energy Materials, vol. 1, XP055246888, 2011, pp. 1215-1219. |
| A. Rowe, et al., “Experimental investigation of a three-material layered active magnetic regenerator”, International Journal of Refrigeration, vol. 29, XP027948436, 2006, pp. 1286-1293. |
| Office dated Dec. 4, 2018, in Chinese Examination Report patent application No. 201580068084.5 with English translation. |
| Number | Date | Country | |
|---|---|---|---|
| 20180005735 A1 | Jan 2018 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62093554 | Dec 2014 | US |
