CN103748424A - System and method for reverse degradation of a magnetocaloric material - Google Patents
System and method for reverse degradation of a magnetocaloric material Download PDFInfo
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- CN103748424A CN103748424A CN201280035141.6A CN201280035141A CN103748424A CN 103748424 A CN103748424 A CN 103748424A CN 201280035141 A CN201280035141 A CN 201280035141A CN 103748424 A CN103748424 A CN 103748424A
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- 230000005291 magnetic effect Effects 0.000 claims abstract description 65
- 238000001816 cooling Methods 0.000 claims abstract description 37
- 230000001172 regenerating effect Effects 0.000 claims abstract description 11
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- 238000011069 regeneration method Methods 0.000 claims description 29
- 230000032683 aging Effects 0.000 claims description 23
- 239000013529 heat transfer fluid Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000012546 transfer Methods 0.000 claims description 11
- 230000007850 degeneration Effects 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
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- 239000012530 fluid Substances 0.000 description 32
- 230000000694 effects Effects 0.000 description 12
- 238000000113 differential scanning calorimetry Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 238000005057 refrigeration Methods 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 238000013459 approach Methods 0.000 description 10
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- 230000006870 function Effects 0.000 description 8
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- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
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- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
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- 229910052779 Neodymium Inorganic materials 0.000 description 1
- FZXTYMGSDGWHLI-UHFFFAOYSA-N O.[Si].[Fe] Chemical compound O.[Si].[Fe] FZXTYMGSDGWHLI-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B21/00—Machines, plants or systems, using electric or magnetic effects
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/012—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials adapted for magnetic entropy change by magnetocaloric effect, e.g. used as magnetic refrigerating material
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B2321/00—Details of machines, plants or systems, using electric or magnetic effects
- F25B2321/002—Details of machines, plants or systems, using electric or magnetic effects by using magneto-caloric effects
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B2321/00—Details of machines, plants or systems, using electric or magnetic effects
- F25B2321/002—Details of machines, plants or systems, using electric or magnetic effects by using magneto-caloric effects
- F25B2321/0022—Details of machines, plants or systems, using electric or magnetic effects by using magneto-caloric effects with a rotating or otherwise moving magnet
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
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- Mechanical Engineering (AREA)
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- General Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Hard Magnetic Materials (AREA)
- Investigating Or Analyzing Materials By The Use Of Magnetic Means (AREA)
Abstract
A method includes identifying at least partial degradation of a magnetocaloric material in a magnetic cooling system, wherein the magnetiocaloric material has a Curie temperature. The method also includes regenerating the magnetocaloric material by maintaining the magnetocaloric material at a regenerating temperature, wherein the regenerating temperature is different from the Curie temperature of the magnetocaloric material.
Description
The cross reference of related application
The application require to submit on July 19th, 2011 the 61st, the priority of 509, No. 381 U.S. Provisional Patent Application, its whole disclosures are incorporated to herein by the mode of quoting in full at this.
Background technology
Provide following description to help reader understanding.The information providing or the list of references of quoting are not counted as prior art.
Ferromagnetic material (for example, iron) comes from the strong interaction in the magnetic field applying the ability that the atomic spin in material structure as one man comes into line itself and the magnetic field applying.Higher than specific temperature (this specified temp is the feature of magnetic material and is called as Curie temperature), thermal agitation stops this consistent spin to be arranged, and becomes very weak with the interaction in applied magnetic field.Higher than Curie temperature, this material is paramagnetic rather than ferromagnetic.Asymptotic Curie temperature, the consistent arrangement of atomic spin in applied magnetic field causes this material magnetic entropy to reduce.If this material is conservation by heat insulation its total entropy that makes, this magnetic entropy reduce by the increase of its hot entropy, compensate, then its temperature raises.Temperature while being exposed to magnetic field raises and is called as magnetothermal effect.When applied magnetic field is removed, magnetic entropy raises, and hot entropy reduces, and the temperature of this material is reduced.
Summary of the invention
An illustrative methods comprises at least part of degeneration of the magneto-caloric material in identification magnetic cooling system, and wherein, this magneto-caloric material has Curie temperature.The method also comprises: by keep this magneto-caloric material this magneto-caloric material of regenerating under regeneration temperature, wherein, this regeneration temperature is different from the Curie temperature of this magneto-caloric material.
Another illustrative methods comprises at least one bed that forms magnetic cooling system, wherein, this at least one bed comprises magneto-caloric material, wherein, this magneto-caloric material has Curie temperature, and wherein, heat-transfer fluid is configured to transfer heat to magneto-caloric material at least one or heat transfer of magneto-caloric material at least one from this at this.The method also comprises that at least one valve of forming this magnetic cooling system is to control flowing of this heat-transfer fluid at least one and heater or heat exchanger by this, wherein, at this, flowing through between at least one and this heater keeps this magneto-caloric material this magneto-caloric material of regenerating to this heat-transfer fluid under regeneration temperature, wherein, this regeneration temperature is different from the Curie temperature of this magneto-caloric material.
An exemplary means comprises heat-transfer fluid and bed, and this comprises the magneto-caloric material with Curie temperature.This bed is configured to allow this heat-transfer fluid to transfer heat to this magneto-caloric material or conducts heat from this magneto-caloric material.This device also comprises heater, and this heater is configured to keep this magneto-caloric material under regeneration temperature and continues a time quantum with this magneto-caloric material of regenerating, and wherein, this regeneration temperature is different from the Curie temperature of this magneto-caloric material.
An example system comprises the first subsystem and the second subsystem.The first subsystem comprises the first heat-transfer fluid and has first of the first magneto-caloric material, and wherein, this first magneto-caloric material has the first Curie temperature.This first subsystem also comprises the first valve, and this first valve is configured to control the first subsystem and works under regeneration mode or refrigerating mode.The second subsystem comprises the second heat-transfer fluid and has second of the second magneto-caloric material, and wherein, this second magneto-caloric material has the second Curie temperature.This second subsystem also comprises the second valve, and this second valve is configured to control this second subsystem and works under regeneration mode or refrigerating mode.
Accompanying drawing explanation
By reference to the accompanying drawings, according to the following description and the appended claims book, aforementioned feature of the present disclosure and further feature will become clearer.Should be appreciated that these figure only describe according to multiple embodiments of the present disclosure, and therefore do not regard its scope that limits as, the disclosure will be by being used accompanying drawing to describe additional features and details.
Fig. 1 is the figure illustrating according to the magnetothermal effect in gadolinium (Gd) of illustrative embodiments.
Fig. 2 is the figure illustrating according to the stage of the active magnetic regenerator circulation of illustrative embodiments.
Fig. 3 illustrates the comparison between isothermal Entropy Changes (left figure) and the thermal capacitance (right figure) in the magnetic field of 1.0 teslas according to the LaFeSiH of illustrative embodiments and Gd.
Fig. 4 illustrates minimum stream temperature in kind of refrigeration cycle and the maximum fluid temperature according to the position in magnetic is refrigeration bed according to illustrative embodiments.
Fig. 5 illustrates compared with having the Magnetic refrigerator of individual layer Gd bed, according to the be of five storeys figure of performance of Magnetic refrigerator of LaFeSiH bed of the tool of illustrative embodiments.
Fig. 6 illustrates according to the differential scanning calorimetry of the brand-new sample of the LaFeSiH of illustrative embodiments (DSC) trace.
Fig. 7 representative is maintained at and approaches its Curie temperature and exceed 1 year later DSC trace according to the material with identical in Fig. 6 of illustrative embodiments.
Fig. 8 is the figure illustrating according to recovering the LaFeSiH of aging division at the temperature of passing through to be exposed to rising of illustrative embodiments.
Fig. 9 is the figure illustrating according to recovering the LaFeSiH of aging division at the temperature of passing through to be exposed to reduction of illustrative embodiments.
Figure 10 is the figure that is operated in the active magnetic cold-storing type refrigeration machine under refrigerating mode according to illustrative embodiments.
Figure 11 is the figure that is operated in the active magnetic cold-storing type refrigeration machine under recovery pattern according to illustrative embodiments.
Figure 12 is according to the figure of the active magnetic regenerator cooling system with two two cross-talk systems of the first illustrative embodiments.
Figure 13 is according to the figure of the active magnetic regenerator cooling system with two two cross-talk systems of the second illustrative embodiments.
The specific embodiment
In the following detailed description, reference forms the accompanying drawing of a part for this detailed description.In these accompanying drawings, unless context separately has regulation, otherwise similar Reference numeral is often referred to similar parts.Illustrative embodiments, accompanying drawing and claims of in detailed description, describing do not mean that restriction.In the case of not departing from the spirit or scope of the theme presenting herein, can utilize other embodiment and can make other change.Will readily appreciate that, as described herein conventionally and can arranging, substitute, combine and design with multiple different configuration in the many aspects of the present disclosure shown in diagram, all these configure be conceived and clearly as a part of this disclosure.
Magnetic refrigerator (MR) uses magnetothermal effect to pump heat and this heat is discharged into hotter environment from colder system.Magnetothermal effect refers to that temperature when material is exposed to magnetic field raises.When removing applied magnetic field, magnetic entropy raises, and hot entropy reduces, and the temperature of material reduces.In Fig. 1, for the magneto-caloric material gadolinium (Gd) of Curie temperature with approximately 60 °F, this variations in temperature is shown.For example, for this material, at first when the temperature of 60 °F, the magnetic field that applies 2 teslas will cause that the temperature of 10 °F raises.When the intensity in applied magnetic field increases, variations in temperature increases.
Modern room temperature MR system can be used active magnetic regenerator (AMR) circulation to carry out cooling.The early implementation of AMR circulation can be referring to U.S. Patent No. 4332135, and its whole disclosures incorporated herein by reference.In one embodiment, as schematically illustrated at Fig. 2, AMR circulation has four-stage.MR system in Fig. 2 comprises porous bed and the heat-transfer fluid of magneto-caloric material (MCM), heat-transfer fluid and a MCM heat exchange when this heat-transfer fluid is flowed through bed.In Fig. 2, the left side of bed is cold side, and the right side of bed is hot side.In alternative embodiment, hot side and cold side can be exchanged.The timing that fluid is mobile and direction (from heat to cold or from being as cold as heat) applying and removing and adjust according to magnetic field.
In the first stage (" magnetization ") of circulation, the fluid in bed is immobilising, applies magnetic field and to MCM, this MCM is heated.In the second stage (" from being as cold as heat flow ") of circulation, keep the magnetic field on bed, at fixed temperature T
cifluid under (cold inlet temperature) is flowed through bed and is pumped to hot side from cold side.When fluid is sent to this next section, this fluid is from this each section heat absorption, makes bed cooling and make fluid heats, and wherein this process is proceeded at higher temperature.This fluid finally reaches temperature T
ho(hot outlet temperature), in hot exit, fluid leaves this bed.Conventionally, this fluid is recycled by hot side heat exchanger, and at hot side heat exchanger place, this fluid is discharged into surrounding environment by its heat.In the phase III (" demagnetization "), fluid flows and is terminated and magnetic field is removed.This causes bed further cooling.In the final stage (" from heat to cold flow ") of circulation, continuing not have under the condition in magnetic field, at fixed temperature T
hithe fluid of (hot inlet temperature) is pumped into cold side from hot effluent through bed.Along with this fluid is by this every section, therefore this fluid is cooled, reach temperature T
co(cold outlet temperature), this temperature T
coit is the minimum temperature that fluid reaches in circulation.Conventionally, this colder fluid is recycled by cold side heat exchanger, at this cold side heat exchanger place, should from refrigeration system, obtain heat compared with cold fluid, and this system is remained under its low temperature.
The required time of four-stage that completes execution AMR circulation is called circulation timei, and the inverse of circulation timei is called as cycle frequency." temperature span " of MR system is defined as T
hi-T
ci, T
hi-T
ciit is the difference of inlet fluid temperature.AMR circulation is similar to simple steam compression cycle, and wherein gas compression (causing gas to be heated) plays magnetized effect, and the free wxpansion of gas (gas temperature is reduced) plays demagnetization.Although Fig. 2 illustrates the work of single MR system, but, in alternative embodiment, can in single system, combine multiple beds (the each AMR circulation that experience is identical) and, to increase cooling capacity, reduce system dimension, or improve in addition the enforcement of AMR circulation.
Conventionally, the magnetic field of 1 tesla of tesla to 2 is used to effectively develop the magnetothermal effect for freezing.This magnetic field is provided by the assembly of strong NdFeB magnet conventionally.The remanent magnetism of the NdFeB magnet of highest ranking is approximately 1.5 teslas.Than the use in this stronger magnetic field, MR performance be can improve, but in order to obtain the magnetic field that exceedes this remanent magnetism, increase magnet size and weight needed greatly (may forbid).Therefore, 1.5 teslas are to provide between MR system dimension and performance the magnetic field intensity of optimum balance substantially.Along with the raising of permanent magnetism technology, can obtain the magnet that is greater than 1.5 tesla's remanent magnetism.In this case, the best field intensity intensity of MR system can correspondingly increase.
Permanent-magnet component is the most expensive parts in MR normally.In order to make full use of the resource of this costliness, the magneto-caloric material using in MR should have the strongest possible magnetothermal effect.This material should also avoid using any poisonous, reactive or rare (therefore expensive) composition.The business use of for example Gd has been got rid of in design above, and Gd is nontoxic, inertia and cheap, but has weak magnetothermal effect.Use the MR system of material that Gd or other have a similar magnetic calorific intensity for commercial applications and Yan Tai great.Lanthanum iron silicon hydrate (LaFeSiH) is one of the most promising magneto-caloric material for business MR system.The description of LaFeSiH can be " Itinerant-electron metamagnetic transition and large magnetocaloric effects in La (Fe referring to the people's such as Fujita title
xsi
1-x)
13compounds and their hydrides " article (Physical Review B67 (2003)), its whole disclosures are incorporated herein by reference.This LaFeSiH material has strong magnetothermal effect.For example, Fig. 3 illustrates two most important measuring of the magnetic calorific intensity of LaFeSiH, that is, and and the isothermal Entropy Changes (left figure) in the magnetic field of 1.0 teslas and thermal capacitance (right figure).For relatively, the identical performance for Gd is also shown.Due to the magnetic calorific intensity greatly strengthening, therefore the MR system of use LaFeSiH can be compacter than using the system of Gd.Although LaFeSiH has the rare-earth metal La (lanthanum) as composition, but, because La is a kind of element the abundantest in thulium, therefore that LaFeSiH remains is cheap.
In most cooling application, temperature span can be very large, is conventionally about 30 ℃ (54 °F) or larger.Although MR system support total span can be very large, but in system bed given axial cross section in temperature in kind of refrigeration cycle, can remain in narrower scope.For example, Fig. 4 illustrates, for the specific MR system that is designed to domestic air conditioner, according to theoretical lowest stream temperature and the highest fluid temperature (F.T.) of theory in kind of refrigeration cycle of the axial location in bed.For this situation, although total moisture content span is 37 ℃, the each axial location in bed has experienced around the variations in temperature of only ± 2 ℃ of its mean values.If this is comprised of single magneto-caloric material, some regions of bed therefore can be in the temperature away from its Curie temperature.These regions of bed are by Entropy Changes little experience and will have low thermal capacitance (see figure 3).These regions will show as more as passive regenerator and very little for the cooling capacity contribution of system.This inefficient use of bed volume can be by being used stratified bed (greatly Enhanced MR systematic function) to avoid.In stratified bed, every one deck contains magneto-caloric material, and the Curie temperature of this magneto-caloric material is matched with the mean temperature of this layer in circulation.By selecting by this way the Curie temperature of layer material, every one deck will have in the strong Entropy Changes of cycle period and large thermal capacitance.Therefore all layers will be contributed on one's own initiative during kind of refrigeration cycle, and this has greatly improved the overall performance of system.Except having strong magnetothermal effect, by changing hydrogen (H) content, to make it be desirable for being used in stratified bed, the Curie temperature of LaFeSiH can easily be controlled at ± 60 ℃ (concern scope of room temperature MR system) between.
In Fig. 5, confirmed the advantage relevant to the stratified bed that uses LaFeSiH, Fig. 5 illustrates for the bed being formed by 5 layers of LaFeSiH, the cooling power of measuring according to temperature span of model machine MR system.In alternative embodiment, can use still less or more layer.For relatively, it also shows under same condition of work, there is the performance of the identical bed of single Gd layer.For example, under the temperature span of 13 ℃, the cooling power that the LaFeSiH bed of layering provides exceedes three times of Gd bed.
Although it is the ideal material for MR that LaFeSiH it seems, but, its unstable properties.Show, when this material preservation this material when approaching very much the temperature of its curie point having been experienced to the variation gradually of its magnetic calorific intensity, referring in the IEEE Intermag conference (Taibei in 2011, Taiwan) the title of the upper A.Barcza occurring of meeting ED-07 etc. be " Stability and magnetocaloric properties of sintered La (Fe; Mn, Si)
13h
zalloys " article (hereinafter to be referred as " A.Barcza etc. ") described in, its whole disclosures are incorporated herein by reference.This variation is easy to observe in differential scanning calorimetry (DSC).Fig. 6 illustrates the DSC trace of the brand-new sample of LaFeSiH, and this trace has single spike.It also shows the width at this peak in DSC trace.In order to compare, Fig. 7 illustrates the DSC trace of same sample after maintenance approaches its Curie temperature to exceed 1 year.When sample remains on the temperature that approaches its Curie temperature, DSC trace shows that the ferromagnetic variation to paramagnetic phase is widened on width and in height reduces.Finally, as shown in the article at Fig. 7 and A.Barcza etc., the initial large and sharp transformation of this material will be divided into two wide and shallow peaks (" aging division ").As shown in the article of as measured in magnetometry and A.Barcza etc., the aging division of DSC trace is accompanied by the reduction of material Entropy Changes.The speed that division occurs depends on temperature.For the LaFeSiH of 2 ℃ of curie points of storage at 2 ℃, peak obviously widen about needs 10 days, the formation at division peak approximately needs 60 days.For the LaFeSiH material of 20 ℃ of curie points 20 ℃ of storages, division peak formed in about 10 days.For the material of 32 ℃ of curie points 32 ℃ of storages, division peak formed in about 5 days.
As long as hydrogen content is lower than 1.5/ formula unit, the ageing process of LaFeSiH seems not rely on synthetic method.Molten by arc, then anneal and in forming the material of 1 to 13 phase, then hydrogenation, find out ageing process several weeks.By melt spinning or atomization by rapid solidification, then anneal a few hours or still less also find out aging fission process in forming the material of 1 to 13 phase, then hydrogenation.At the Different L aFeSiH sample with slightly different composition (as La
1.29(Fe
0.88si
0.12)
13h
yand La
1.2(Fe
0.888si
0.112)
13h
y) in find out aging fission process.At Pr
0.6la
0.6(Fe
0.888si
0.112)
13h
yin sample, also find out aging fission process, wherein Pr is replaced to increase magnetic calorific intensity by some La.Therefore, aging fission process can occur in RE (TM conventionally
xsi
1-x)
13h
y(wherein RE represents rare earth element to material, as La, Ce, Pr or Nd; TM represents transition metal, as Fe, Cr, Mn or Ni; X<0.15, y<1.5) in the magneto-caloric material of form.In the exemplary embodiment, the value of y can be between about 0.8 and 1.5.Alternatively, can use the y value of different range.As discussed herein, can use different y values to produce the magneto-caloric material with different Curie temperature.
When magneto-caloric material is used in MR system, magneto-caloric material will inevitably be exposed to the temperature that approaches its Curie temperature.In fact, in stratified bed, the material in layer is selected to has the Curie temperature equating with the mean temperature of this layer drawing in MR cycle period.Thereby, if use partially hydrogenated LaFeSiH in MR system, or more general RE (TM
xsi
1-x)
13h
y, its magnetic heating performance will be degenerated in time.Although partially hydrogenated RE (TM
xsi
1-x)
13h
ymaterial has the obvious advantage that exceedes other magneto-caloric materials, but partially hydrogenated RE (TM
xsi
1-x)
13h
ythis degeneration of the magnetic heating performance of material can hinder its use in commercial MR system potentially.
Applicant has been found that as the RE (TM degenerating
xsi
1-x)
13h
yfor example, when material is maintained at the temperature (, higher or lower temperature) away from its curie point subsequently, degenerative process reverses and the performance of final material turns back to its original state.In addition, applicant's discovery, as shown in Figure 8, material recovers to carry out quickly under higher temperature.The material (being LaFeSiH) with the Curie temperature of 26.7 ℃ by storage at this temperature, exceed 1 year and aging division until as reach 14 ℃ by the measured magnetic transition width of DSC.As being 2.1 ℃ by the measured this initial magnetic transition width of DSC.Then the material of degenerating is exposed under different temperatures (that is, 38.5 ℃, 44 ℃, 60 ℃ and 100 ℃) as shown in FIG..At 44 ℃, exposing about 6 days is enough to material to return to its original state completely, and at 60 ℃, exposes about 3 days and be enough to material to return to its original state completely.At 100 ℃, expose less than the reverse completely that is enough to obtain aging division for 1 day.Applicant also finds Pr
0.5la
0.5(Fe
1-xsi
x)
13h
yaging division to degenerate be also completely reversibility by this heat treatment.As shown in Figure 9, by being exposed to the temperature of reduction, also obtained the recovery of the initial sharp magnetic transition of the LaFeSiH of aging division, but process is carried out more slowly.LaFeSiH material has the magnetic transition of 1.2 ℃ of width at first, and LaFeSiH material is maintained at and approaches its curie point of 37 ℃ after 6 days, and magnetic transition is broadened to 4.4 ℃.By keeping material to be restored at 5 ℃.Within 100 days, recovered afterwards.In the exemplary embodiment, the regeneration temperature that is used for recovering magneto-caloric material can start to leave lower than hydrogen the maximum temperature of magneto-caloric material.This maximum temperature is approximately 180 ℃.
Can be fully reversible in relatively simple mode because aging division is degenerated, so RE (TM
xsi
1-x)
13h
ymaterial can be used in the MR system of suitably changing, and this has formed the basis of theme described herein.Under the normal mode of MR system works of stratified bed with magneto-caloric material, material layer approaches its Curie temperature separately by keeping, and this will cause magneto-caloric material variation.In addition,, when system is not worked, curie point approaches the magneto-caloric material part of environment temperature also can variation.Therefore, applicant has developed a kind of improved MR system, and this improved MR system is configured to keep at the temperature that is different from magneto-caloric material Curie temperature any aging division that magneto-caloric material layer can occur with reverse degenerate and recover its whole magnetothermal effect.The maintained temperature of magneto-caloric material can be higher or lower than the Curie temperature of magneto-caloric material, according to required regeneration rate, and power system capacity etc., the maintained temperature of magneto-caloric material can differ 10 ℃, 25 ℃, 50 ℃, 100 ℃ etc. with Curie temperature.In the exemplary embodiment, the maintained temperature of magneto-caloric material can differ about 10 ℃ with Curie temperature.
In an illustrative embodiments, MR system is used RE (TMxSi1
-x) 13H
yas magneto-caloric material and there is the heating element heater of access in running system.In addition, for example, when MR system is when idle (, at the residential air conditioner machine at night), heating element heater can be activated.Then MR system makes the Fluid Circulation being heated by magneto-caloric material, fully reverses any aging division that high-temperature process may occur due to last time.
Conventionally at cold heat exchanger (CHEX), locating to absorb heat and at heat exchanger (HHEX), locating under the particular case of the MR system of discharging heat, heater can access in parallel with this cold heat exchanger.As shown in Figure 10, under the refrigerating mode of standard, stream is directed to by CHEX and HHEX.As shown in Figure 10, AMR type refrigeration machine is worked under refrigerating mode, and this refrigeration machine comprises the bed of one or more demagnetizations, and these are to providing cooling with the cold heat exchanger of load thermo-contact to be cooled.One or more magnetized beds are discharged heat to heat exchanger.In one embodiment, each bed comprises having approximately from T
cto T
hrE (the TM of the curie point in scope
xsi
1-x)
13h
ylayer, wherein T
h>T
c.
Figure 11 is illustrated in the AMR type refrigeration machine of working under recovery pattern.In one embodiment, the heater of connecting with multiple heats these high-Curie-points to the material than in these and exceeds on 10 ℃, and these heat exchangers are bypassed.Discuss in more detail as shown in Figure 11 and below, when recovery pattern starts, valve switches to stream away from cold heat exchanger and by stream and is redirected heater.When recovering pattern, can add the second valve to switch stream away from heat exchanger (also seeing Figure 11).These two valves are the heat isolation of MR system, thereby use less heater power can be heated the temperature higher than approximately 10 ℃ of the curie points of all magneto-caloric materials in system.If suspend magnet movement or fluid during recovery pattern, flow backwards, AMR cycling is suspended, and this has reduced the amount that remains on needed heater power under recovery pattern.Because magnet movement and fluid flow backwards, utilize extra electrical power, so suspend these operations, be also reduced in the quantity of power that under recovery pattern, system consumes.
In alternative embodiment, cooling system is except having heating element heater, and cooling system can also comprise two independently MR subsystems.The one MR subsystem can provide cooling as Figure 10, and simultaneously the bed experience of the second subsystem as the heat treatment of Figure 11, to reverse aging division.For example, after certain time under these operating conditions (, 1 hour, 2 hours, 4 hours, 12 hours etc.), can switch MR subsystem, the second subsystem provides cooling and the first subsystem experience heat treatment.In the period of peak value cooling requirement, two MR subsystems can provide cooling power.In another alternative embodiment, this system can be incorporated to the subsystem more than two, and some subsystems provide cooling power and all the other subsystem experience heat treatments.
In another alternative embodiment, cooling system can have two sections, the AMR bed that each section comprises layering.Cold section can have from T
cto T
mthe Curie temperature of scope, and hot arc can have from T
mto T
hthe Curie temperature of scope, wherein T
h>T
m>T
c.In air conditioner is implemented, T
ccan there is the value of 10 ℃, T
mcan there is the value of 25 ℃, T
hcan there is the value of 40 ℃.At alternative embodiment and/or in implementing, can use different temperature values.When wanting to recover hot arc magneto-caloric material, can under refrigerating mode, work for cold section, produce temperature and approach T
ccold outlet fluid stream.This cold fluid cold side heat exchanger of not flowing through, but can be directed to by hot arc to obtain approaching T
chot arc temperature.Because T
cfar below all Curie temperature in hot arc, so be exposed to this temperature, can reverse any aging division in hot arc.Similarly, when needs recover cold section of magneto-caloric material, hot arc can work and therefore can produce temperature and approach T under refrigerating mode
hheat outlet fluid stream.This hot fluid hot side heat exchanger of not flowing through, but can be directed to logical super cooled sect so that its temperature approaches T
h.Because, far above all Curie temperature in cold section, being exposed to this temperature, this temperature can reverse any aging division of cold section of material.
In another alternative embodiment, system can comprise two independently MR subsystems, and each subsystem has as in the above-described embodiment two sections, i.e. hot arc and cold section.When needs are during high cooling power, as shown in Figure 12, two subsystems can parallel running, and each subsystem provides cooling.In Figure 12, the section that is connected to pump and hot HEX has a LaFeSiH as magneto-caloric material, and its curie point is from T
hto T
mscope in.The section that is connected to cold HEX has curie point from T
mto T
cscope in LaFeSiHMCM.In the exemplary embodiment, curie point is at T
mmCM be positioned at be connected to another bed end.As shown in figure 13, when the less cooling power of needs, a subsystem may operate under refrigerating mode, and another subsystem may operate under recovery pattern to repair the performance of its magneto-caloric material.In Figure 13, lower subsystem cooling power is provided and upper subsystem in recovery pattern.From at least a portion of the cold outlet fluid stream of the demagnetization bed of lower subsystem, turn to the hot arc bed of upper subsystem.Meanwhile, a part for the heat of the magnetizing bed of lower subsystem outlet fluid stream turns to cold section of bed of subsystem.Can also change this embodiment to be incorporated to the subsystem more than two, some subsystems provide cooling power and the heat treatment of remaining subsystem experience.At this generally, each subsystem can have as described above two sections.
In another alternative embodiment, possible multiple beds of magnetic refrigerating system can be designed to easily removable and replaceable from system.The bed of therefore having degenerated due to aging division can be removed and with brand-new bed replacement.In the isolated system away from magnetic refrigerating system physically, by being exposed to the temperature of Curie temperature of all layers that fully contain away from them, the bed of degeneration can turn back to brand-new state.For example, this device can be the simple flow circuits with heater, and it can make fluid at high temperature circulate through the bed of degenerating, or this device can be to make bed keep the baking oven of high temperature.Once return to brand-new state, these beds can be reinstalled in magnetic refrigerating system.
Any operation described herein can be undertaken by computing system, and this computing system comprises processor, memory, transmitter, receiver, display, user interface and/or other machine elements known to persons of ordinary skill in the art.Can use the computing system of any type known to persons of ordinary skill in the art.In one embodiment, any operation described herein can be changed into the instruction being stored on computer-readable medium by code.Computing system can be utilized to carry out these instructions, thereby these operations are performed.
Embodiment
For the impact of verifying that aging division is degenerated on magnetic refrigerator performance, and in order to verify that high-temperature process is effectively for reversing this degeneration, the bed of magnetic refrigerator is loaded five layers of La (Fe
0.885si
0.115) H
ymaterial, every one deck has different y values and therefore has different curie points.The curie point of these layers is initially 8 ℃, 11 ℃, 15 ℃, 18 ℃ and 21 ℃.Under the operating condition of standard group, tested machine, wherein cycle frequency is 3.33Hz, and flow rate is 6 liters/min, and hot inlet temperature is 25 ℃, and the cooling load being provided by electric heater is 400 watts.Before as MR operation, the LaFeSiH in bed is full of and reaches 80 hours so that material reaches its original state by the aqueous fluids of 35 ℃.The temperature span under reference operating condition with the machine of brand-new material is 13.4 ℃.Then make this machine under the environment temperature of 22 ℃ in off working state, continue 10 days.In this state, Curie temperature is that the material expectation of 18 ℃ and 21 ℃ can be experienced aging division and degenerates, and in fact, at the temperature span under reference operating condition of this 10 days machines after treatment, drops to only 2.9 ℃.Then LaFeSiH MCM is full of and reaches 19 hours so that material reaches its original state by the aqueous fluids of 50 ℃, and the machine under AMR pattern is that 400 watts and hot inlet temperature are that temperature span under the standard conditions of 25 ℃ is through being measured as 13.2 ℃ in cooling load.Therefore, make LaFeSiH MCM continue 19 hours in exceed temperature on 10 ℃ than the curie point of material, can be MCM being remained on to the performance of recovering MCM after the performance occurring when approaching its curie point and continuing 10 days significantly reduces.
Theme described herein illustrates the different parts that comprise in different miscellaneous parts or the different parts that connect from different miscellaneous parts sometimes.The structure that should be appreciated that such description is exemplary, in fact, can implement to realize multiple other structures of identical function.In concept meaning, consider, realize identical function parts any layout effectively " association " make to realize required function.Therefore, any two parts that combine of realizing specific function herein can be regarded as " association " in making each other to realize required function, and irrelevant with structure or intermediate member.Equally, so associated any two parts also can be regarded as " being operably connected " or " being operationally coupled " in each other to realize required function, and, can be so associated any two parts also can be regarded as " operationally can be coupled " in each other to realize required function.The specific embodiment that operationally can be coupled include but not limited to physically can be coupled and/or physically mutual parts and/or wireless can be alternately and/or the parts of wireless interaction and/or logic is mutual and/or logic can be mutual parts.
About the use of any plural number and/or odd number wording substantially herein, those skilled in the art can be based on context and/or purposes from plural number, transform to odd number and/or transform to plural number from odd number.For clarity sake, enumerated clearly the conversion of multiple singular/plural herein.
It will be appreciated by those skilled in the art that, in general, term used herein, particularly appending claims (for example, the main body of appended claim) in use term be conventionally intended to represent " opening " term (for example, term " comprises " and is to be understood as " including but not limited to ", and term " has " and is to be understood as " at least having ", term " comprise " and should be construed as " including but not limited to " etc.).Those skilled in the art should also be understood that if be intended to quote the claim of optional network specific digit, will clearly state in the claims, and when there is no this quoting, there is no such intention.For example, in order to help to understand, appended claims can comprise for introducing introductory phrase " at least one " that claim quotes and the use of " one or more ".But, the use of this phrase does not should be understood to hint, indefinite article " one " or " one " require any specific rights of the claim that comprises this introducing to be restricted to only to comprise an invention of quoting like this, even for example, when identical claim comprises introductory phrase " one or more " or " at least one " and indefinite article for example " one " or " one " (, " one " and/or " one " should be construed as representing " at least one " or " one or more " conventionally); For the use of the definite article of quoting of introducing claim, like this equally.In addition, even if enumerated clearly the claim of quoting of optional network specific digit, those skilled in the art will recognize that, this narration (is for example to be understood as the numeral at least quoted conventionally, without the basic narration of other modifier " quoting for two ", at least two of ordinary representations are quoted, or two or more quoting).In addition, in use, be similar to the idiom of " at least one in A, B and C etc. ", in general, this structure will be understood this idiom (for example, " system has at least one in A, B and C " will include but not limited to following system: have separately A, have B separately, have C separately, have A and B simultaneously, have A and C simultaneously, have B and C and/or have A, B and C etc. simultaneously simultaneously) In the view of those skilled in the art.In use, be similar to the idiom of " at least one in A, B or C etc. ", in general, this structure will be understood this idiom (for example, " at least one 〃 that system has in A, B or C will include but not limited to following system: have separately A, have B separately, have C separately, have A and B simultaneously, have A and C simultaneously, have B and C and/or have A, B and C etc. simultaneously simultaneously) In the view of those skilled in the art.Those skilled in the art will also be understood that, in fact, no matter be in description, claim or accompanying drawing, any extract word and/or the phrase that represents two or more substituting terms is all to be understood as and provided the possibility that comprises one of these terms, these terms any or two terms.For example, phrase " A or B " will be understood as that the possibility that comprises " A " or " B " or " A and B ".
For the purpose of illustration and description, provided the above-mentioned explanation of illustrative embodiments.With regard to disclosed clear and definite form, be not intended to exhaustive or restriction, according to above-mentioned instruction, can make multiple modification and modification or can obtain multiple modification and modification from the enforcement of disclosed embodiment.Be noted that scope of the present invention is to be limited by appending claims and equivalent thereof.
Claims (22)
1. a method, comprising:
At least part of degeneration of the magneto-caloric material in identification magnetic cooling system, wherein, described magneto-caloric material has Curie temperature; With
By described magneto-caloric material being remained under regeneration temperature, make described magneto-caloric material regeneration, wherein, described regeneration temperature is different from the described Curie temperature of described magneto-caloric material.
2. the method for claim 1, wherein described regeneration temperature and described Curie temperature differ at least 5 degrees Celsius.
3. the method for claim 1, wherein described regeneration temperature and described Curie temperature differ at least 10 degrees Celsius.
4. the method for claim 1, wherein described magneto-caloric material comprises hydrogen, and wherein said regeneration temperature is lower than maximum temperature, and described maximum temperature is at least a portion of described hydrogen temperature when starting to leave described magneto-caloric material.
5. the method for claim 1, wherein described magneto-caloric material comprises RE (TM
xsi
y)
13h
z, wherein RE is that rare earth element and TM are transition metal.
6. the method for claim 1, also comprises: while keeping described magneto-caloric material under described regeneration temperature, suspend the active magnetic regenerator circulation of described magnetic cooling system.
7. the method for claim 1, also comprises:
From described magnetic cooling system, remove described magneto-caloric material, make to keep described magneto-caloric material under the described regeneration temperature away from described magnetic cooling system; With
Described magneto-caloric material is replaced by the magneto-caloric material of regenerating.
8. the method for claim 1, wherein regeneration comprises the aging division that reverses described magneto-caloric material.
9. a method, comprising:
Form at least one bed of magnetic cooling system, wherein, described at least one bed comprises magneto-caloric material, described magneto-caloric material has Curie temperature, wherein, heat-transfer fluid is configured to transfer heat to described described magneto-caloric material at least one or conducts heat from described described magneto-caloric material at least one;
At least one valve that forms described magnetic cooling system is to control described heat-transfer fluid flow through described at least one bed and heater or heat exchanger, wherein, described heat-transfer fluid flowing through between described at least one and described heater keeps the described magneto-caloric material described magneto-caloric material of regenerating under regeneration temperature, and described regeneration temperature is different from the described Curie temperature of described magneto-caloric material.
10. method as claimed in claim 9, wherein, the mobile of described heat-transfer fluid between described at least one and described heat exchanger makes described magneto-caloric material cooling.
11. methods as claimed in claim 9, wherein, described at least one bed comprises multiple layers, wherein, described at least one each layer comprises the different magneto-caloric materials with different Curie temperature, wherein, at the described different Curie temperature of giving the described different magneto-caloric materials in given layer, are the described mean temperatures to given layer in active magnetic regenerator cycle period.
12. 1 kinds of devices, comprising:
Heat-transfer fluid;
Bed, described bed comprises the magneto-caloric material with Curie temperature, wherein, described bed is configured to allow described heat-transfer fluid to transfer heat to described magneto-caloric material or conducts heat from described magneto-caloric material; With
Heater, described heater configuration becomes to keep under regeneration temperature described magneto-caloric material and continues a time quantum, and with the described magneto-caloric material of regenerating, wherein, described regeneration temperature is different from the Curie temperature of described magneto-caloric material.
13. devices as claimed in claim 12, wherein, described heater is configured to by the described bed of described heat-transfer fluid heating.
14. devices as claimed in claim 12, wherein, described regeneration temperature is greater than described Curie temperature.
15. devices as claimed in claim 12, wherein, described bed comprises the multiple magneto-caloric material with different Curie temperature, and described regeneration temperature is greater than the high-curie temperature in described different Curie temperature.
16. devices as claimed in claim 12, wherein, described heater is away from described bed, and described bed is configured to temporarily remove for regenerating by described heater from described device.
17. 1 kinds of heat transfer systems, comprising:
The first subsystem, comprising:
The first heat-transfer fluid;
First, described the first bed accessory has the first magneto-caloric material, and wherein, described the first magneto-caloric material has the first Curie temperature; With
The first valve, described the first valve configurations becomes to control described the first subsystem and under regeneration mode, works or work under refrigerating mode; With
The second subsystem, comprising:
The second heat-transfer fluid;
Second, described the second bed accessory has the second magneto-caloric material, and wherein, described the second magneto-caloric material has the second Curie temperature; With
The second valve, described the second valve is configured to control described the second subsystem and under regeneration mode, works or work under refrigerating mode.
18. heat transfer systems as claimed in claim 17, wherein:
During the first period, described the first valve is configured to control that described the first subsystem is worked under described refrigerating mode and described the second valve is configured to control described the second subsystem and works under described regeneration mode; With
During the second period, described the first valve is configured to control that described the first subsystem is worked under described regeneration mode and described the second valve is configured to control described the second subsystem and works under described refrigerating mode.
19. heat transfer systems as claimed in claim 17, wherein, during the given period, described the first valve is configured to control that described the first subsystem is worked under described refrigerating mode and described the second valve is configured to control described the second subsystem and works under described refrigerating mode.
20. heat transfer systems as claimed in claim 17, wherein:
Described first comprises the first multilayer, and wherein, each layer of described first comprises the different magneto-caloric materials with different Curie temperature, and described the first subsystem comprises cold section, makes the different Curie temperature of the described different magneto-caloric materials in described the first multilayer at T
cand T
mbetween scope in; With
Described second comprises the second multilayer, and wherein, each layer of described second comprises the different magneto-caloric materials with different Curie temperature, and described the second subsystem comprises hot arc, makes the different Curie temperature of the described different magneto-caloric materials in described the second multilayer at T
mand T
hbetween scope in, wherein, T
h>T
m>T
c.
21. heat transfer systems as claimed in claim 20, wherein, when working under described refrigerating mode for described cold section, described the first heat-transfer fluid is in temperature T
c, at least one valve in described the first valve and described the second valve guides in described temperature T
cunder described the first heat-transfer fluid by described hot arc with the described hot arc of regenerating.
22. heat transfer systems as claimed in claim 20, wherein, when described hot arc is worked under described refrigerating mode, described the second heat-transfer fluid is in temperature T
h, and at least one valve in described the first valve and described the second valve guides in described temperature T
hdescribed the second heat-transfer fluid by described cold section to regenerate described cold section.
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| US201161509381P | 2011-07-19 | 2011-07-19 | |
| US61/509,381 | 2011-07-19 | ||
| PCT/US2012/047168 WO2013012908A1 (en) | 2011-07-19 | 2012-07-18 | System and method for reverse degradation of a magnetocaloric material |
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| CN103748424A true CN103748424A (en) | 2014-04-23 |
| CN103748424B CN103748424B (en) | 2016-03-16 |
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| CN201280035141.6A Expired - Fee Related CN103748424B (en) | 2011-07-19 | 2012-07-18 | For reversing the system and method that magneto-caloric material is degenerated |
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| EP (1) | EP2734796A4 (en) |
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| MX (1) | MX339024B (en) |
| RU (1) | RU2014105818A (en) |
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- 2012-07-18 CN CN201280035141.6A patent/CN103748424B/en not_active Expired - Fee Related
- 2012-07-18 KR KR1020147004162A patent/KR20140089508A/en not_active Application Discontinuation
- 2012-07-18 RU RU2014105818/06A patent/RU2014105818A/en not_active Application Discontinuation
- 2012-07-18 JP JP2014521728A patent/JP2014521050A/en active Pending
- 2012-07-18 EP EP12814189.2A patent/EP2734796A4/en not_active Withdrawn
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Also Published As
| Publication number | Publication date |
|---|---|
| MX2014000602A (en) | 2014-07-09 |
| KR20140089508A (en) | 2014-07-15 |
| EP2734796A1 (en) | 2014-05-28 |
| CN103748424B (en) | 2016-03-16 |
| MX339024B (en) | 2016-05-05 |
| WO2013012908A1 (en) | 2013-01-24 |
| JP2014521050A (en) | 2014-08-25 |
| RU2014105818A (en) | 2015-08-27 |
| BR112014000922A2 (en) | 2017-02-14 |
| US20130019610A1 (en) | 2013-01-24 |
| EP2734796A4 (en) | 2015-09-09 |
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