CN103748424B - For reversing the system and method that magneto-caloric material is degenerated - Google Patents

For reversing the system and method that magneto-caloric material is degenerated Download PDF

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CN103748424B
CN103748424B CN201280035141.6A CN201280035141A CN103748424B CN 103748424 B CN103748424 B CN 103748424B CN 201280035141 A CN201280035141 A CN 201280035141A CN 103748424 B CN103748424 B CN 103748424B
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magneto
caloric material
temperature
heat
bed
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CN103748424A (en
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卡尔·B·齐姆
史蒂文·A·雅各布斯
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Astronics Corp
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    • 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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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Hard Magnetic Materials (AREA)
  • Investigating Or Analyzing Materials By The Use Of Magnetic Means (AREA)

Abstract

One method, comprising: at least part of degeneration identifying the magneto-caloric material in magnetic cooling system, wherein this magneto-caloric material has Curie temperature.The method also comprises: by keeping magneto-caloric material to regenerate magneto-caloric material under regeneration temperature, wherein this regeneration temperature is different from the Curie temperature of this magneto-caloric material.

Description

For reversing the system and method that magneto-caloric material is degenerated
The cross reference of related application
This application claims the priority of the 61st, 509, No. 381 U.S. Provisional Patent Application submitted on July 19th, 2011, its whole disclosure is incorporated to herein by the mode quoted in full at this.
Background technology
There is provided following description to help reader understanding.The information provided or the bibliography quoted are not counted as prior art.
Ferromagnetic material (such as, iron) and the strong interaction in magnetic field applied come from atomic spin in material structure as one man by ability that itself comes into line with the magnetic field applied.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 alignment, becomes very weak with the interaction in applied magnetic field.Higher than Curie temperature, this material is paramagnetic instead of 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, then this magnetic entropy the increase being reduced by its hot entropy and compensate, then its temperature raise.Temperature when 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 identified in magnetic cooling system, and wherein, this magneto-caloric material has Curie temperature.The method also comprises: regenerate this magneto-caloric material by keeping this magneto-caloric material under regeneration temperature, and wherein, this regeneration temperature is different from the Curie temperature of this magneto-caloric material.
Another illustrative methods comprises at least one bed forming 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 the magneto-caloric material at this at least one or the heat transfer of the magneto-caloric material from this at least one.The method also comprise form this magnetic cooling system at least one valve to control the flowing of this heat-transfer fluid at least one and heater or heat exchanger by this, wherein, this heat-transfer fluid flowing through at this between at least one and this heater keeps this magneto-caloric material to regenerate this magneto-caloric material 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 conduct 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 to regenerate this magneto-caloric material, 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.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 first subsystem and works under regeneration mode or refrigerating mode.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, preceding feature of the present disclosure and further feature will become clearer.Should be appreciated that these figure only describe according to multiple embodiment of the present disclosure, and therefore do not regard as and limit its scope, the disclosure will describe additional features and details by using accompanying drawing.
Fig. 1 is the figure of the magnetothermal effect in gadolinium (Gd) illustrated according to illustrative embodiments.
Fig. 2 is the figure in the stage of the active magnetic regenerator cycle illustrated according to illustrative embodiments.
Fig. 3 illustrates according to the comparison between isothermal Entropy Changes (left figure) in the magnetic field of 1.0 teslas of LaFeSiH and Gd of illustrative embodiments and thermal capacitance (right figure).
Fig. 4 illustrate according to illustrative embodiments according to minimum stream temperature in kind of refrigeration cycle of position in magnetic is refrigeration bed and maximum fluid temperature.
Fig. 5 illustrates compared with having the Magnetic refrigerator of individual layer Gd bed, the figure of performance of Magnetic refrigerator of the LaFeSiH bed that is of five storeys according to the tool of illustrative embodiments.
Fig. 6 illustrates differential scanning calorimetry (DSC) trace of the brand-new sample of the LaFeSiH according to illustrative embodiments.
Fig. 7 representative is maintained at close to its Curie temperature DSC trace later more than a year according to the material identical with Fig. 6 of illustrative embodiments.
Fig. 8 illustrates the figure by recovering the LaFeSiH of aging division at the temperature that is exposed to rising according to illustrative embodiments.
Fig. 9 illustrates the figure by recovering the LaFeSiH of aging division at the temperature that is exposed to reduction according to illustrative embodiments.
Figure 10 is the figure of the work active magnetic cold-storing type refrigeration machine in a cooling mode according to illustrative embodiments.
Figure 11 is the figure of the work active magnetic cold-storing type refrigeration machine in recovery mode according to illustrative embodiments.
Figure 12 is the figure with the active magnetic regenerator cooling system of two two cross-talk systems according to the first illustrative embodiments.
Figure 13 is the figure with the active magnetic regenerator cooling system of two two cross-talk systems according to the second illustrative embodiments.
Detailed description of the invention
In the following detailed description, with reference to the accompanying drawing of a part for this detailed description of formation.In the drawings, unless the context requires otherwise, otherwise similar Reference numeral is often referred to similar parts.The illustrative embodiments described in detailed description, accompanying drawing and claims do not mean that restriction.When not departing from the spirit or scope of the theme presented herein, other embodiment can be utilized and other change can be made.Will readily appreciate that, the many aspects of the present disclosure as described and shown in the example shown herein usually can arrange, substitute, combine and design with multiple different configuration, and all these configure is conceived and clearly as a part of this disclosure.
Magnetic refrigerator (MR) uses magnetothermal effect to pump heat and by this heat dissipation to hotter environment from colder system.Temperature when magnetothermal effect refers to that 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 for the magneto-caloric material gadolinium (Gd) of Curie temperature with about 60 °F, this variations in temperature is shown.Such as, for this material at first when the temperature of 60 °F, the magnetic field applying 2 teslas will cause the temperature of 10 °F to raise.When the intensity in applied magnetic field increases, variations in temperature increases.
Modern room temperature MR system can use active magnetic regenerator (AMR) to circulate and perform cooling.The early implementation of AMR circulation can see U.S. Patent No. 4332135, and its whole disclosure incorporated herein by reference.In one embodiment, as schematically shown 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 flows 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 of fluid flowing and direction (from heat to cold or from being as cold as heat) adjust according to the applying in magnetic field and removing.
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) flows through bed from cold side and is pumped to hot side.When fluid is sent to this next section, this fluid is from this each section heat absorption, and make bed cool and make fluid heats, wherein this process proceeds at a higher temperature.This fluid finally reaches temperature T ho(hot outlet temperature), in hot exit, fluid leaves this bed.Usually, this fluid is recycled by hot side heat exchanger, at this fluid of heat exchanger place, hot side by its heat dissipation to surrounding environment.In the phase III (" demagnetization "), fluid flowing is terminated and magnetic field is removed.This causes bed to cool further.In the final stage (" from heat to cold flow ") of circulation, continuing under the condition not having magnetic field, at fixed temperature T hithe fluid of (hot inlet temperature) is pumped into cold side by from hot effluent through bed.Along with this fluid is by this every section, therefore this fluid is cooled, and reaches temperature T co(cold outlet temperature), this temperature T coit is the minimum temperature that fluid reaches in the circulating cycle.Usually, this colder fluid is recycled by cold side heat exchanger, at this cold side heat exchanger place this comparatively cold fluid from refrigeration system obtain heat, under making this system remain on its low temperature.
The time needed for four-stage completing 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 fluid inlet 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, multiple bed (the AMR circulation that each experience is identical) can be combined, to increase cooling capacity, reduce system dimension in single system, or improve the enforcement of AMR circulation in addition.
Usually, 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 usually.The remanent magnetism of the NdFeB magnet of highest ranking is approximately 1.5 teslas.The use in the magnetic field stronger than this can improve MR performance, but in order to obtain the magnetic field exceeding this remanent magnetism, needs greatly (may forbid) increase magnet size and weight.Therefore, 1.5 teslas are to provide the magnetic field intensity of optimum balance substantially between MR system dimension and performance.Along with the raising of permanent magnet technology, the magnet being greater than 1.5 tesla's remanent magnetism can be obtained.In this case, the best field strength of MR system can correspondingly increase.
The parts that permanent-magnet component is normally the most expensive in MR.In order to make full use of the resource of this costliness, the magneto-caloric material used in MR should have the strongest possible magnetothermal effect.This material also should avoid using any poisonous, reactive or rare (therefore expensive) composition.The business that design above eliminates such as Gd uses, and Gd is nontoxic, inertia and cheap, but has weak magnetothermal effect.Use Gd or other MR systems with the material of similar magnetic calorific intensity for commercial applications 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-electronmetamagnetictransitionandlargemagnetoc aloriceffectsinLa (Fe see the title of the people such as Fujita xsi 1-x) 13compoundsandtheirhydrides " article (PhysicalReviewB67 (2003)), its whole disclosure is incorporated herein by reference.This LaFeSiH material has strong magnetothermal effect.Such as, Fig. 3 illustrates that two of the magnetic calorific intensity of LaFeSiH are most importantly measured, that is, the isothermal Entropy Changes (left figure) in the magnetic field of 1.0 teslas and thermal capacitance (right figure).In order to compare, the identical performance for Gd is also shown.Due to the magnetic calorific intensity greatly strengthened, 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 LaFeSiH remains cheap.
In most cooling application, temperature span can be very large, is usually about 30 DEG C (54 °F) or larger.Although the total span that MR system is supported can be very large, but the temperature in the given axial cross section of bed in system can remain in narrower scope in kind of refrigeration cycle.Such as, Fig. 4 illustrates, for the specific MR system being designed to domestic air conditioner, according to the theoretical lowest stream temperature in kind of refrigeration cycle and the highest fluid temperature (F.T.) of theory of the axial location in bed.For this situation, although total moisture content span is 37 DEG C, each axial location in bed experienced by the variations in temperature around its mean value only ± 2 DEG C.If this is made up of single magneto-caloric material, then therefore some regions of bed can be in the temperature away from its Curie temperature.These regions of bed will experience little Entropy Changes and will have low thermal capacitance (see figure 3).These regions are by very little for the cooling capacity contribution shown as more as passive regenerator and for system.This poor efficiency of bed volume uses can be avoided by using stratified bed (very big Enhanced MR systematic function).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 the circulating cycle.By selecting the Curie temperature of layer material by this way, 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, this considerably improves the overall performance of system.Except having strong magnetothermal effect, make it be desirable for being used in stratified bed by changing hydrogen (H) content, the Curie temperature of LaFeSiH can easily control between ± 60 DEG C (concern scope of room temperature MR system).
Confirm the advantage relevant to using the stratified bed of LaFeSiH in Figure 5, Fig. 5 illustrates the bed for being formed by 5 layers of LaFeSiH, the cooling power measured according to temperature span of model machine MR system.In alternative embodiment, less or more layer can be used.In order to compare, it also shows under same condition of work, there is the performance of the identical bed of single Gd layer.Such as, under the temperature span of 13 DEG C, the cooling power that the LaFeSiH bed of layering provides is more than three times of Gd bed.
Although it is ideal material for MR that LaFeSiH it seems, but, its unstable properties.Show, when by this material preservation in the temperature very close to its curie point time this material experienced by the variation gradually of its magnetic calorific intensity, see in the IEEE Intermag conference (Taibei in 2011, Taiwan) meeting ED-07 on the title of A.Barcza etc. that occurs be " StabilityandmagnetocaloricpropertiesofsinteredLa (Fe; Mn, Si) 13h zalloys " article (hereinafter referred to as " A.Barcza etc. ") described in, its whole disclosure is 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 illustrate same sample keep close to its Curie temperature more than 1 year after DSC trace.When sample remains on the temperature close to its Curie temperature, DSC trace shows that the ferromagnetic change to paramagnetic phase is widened and in height reduces on width.Finally, as shown in the article of Fig. 7 and A.Barcza etc., initial large of this material and the transformation of point will be divided into two wide and shallow peaks (" aging division ").Measured by magnetometry and as shown in the article of A.Barcza etc., the aging division of DSC trace is along with the reduction of material Entropy Changes.The speed that division occurs depends on temperature.For the LaFeSiH of the 2 DEG C of curie points stored at 2 DEG C, obviously widening of peak approximately needs 10 days, and the formation at division peak approximately needs 60 days.For the LaFeSiH material of the 20 DEG C of curie points stored at 20 DEG C, division peak was formed in about 10 days.For the material of the 32 DEG C of curie points stored at 32 DEG C, division peak was formed in about 5 days.
As long as hydrogen content is lower than 1.5/ formula unit, then the ageing process of LaFeSiH seems not rely on synthetic method.Anneal several weeks to find out ageing process in the material forming 1 to 13 phase, then hydrogenation being melted by arc, then.By melt spinning or atomization by rapid solidification, then anneal a few hours or less with the material forming 1 to 13 phase, then hydrogenation in also find out aging fission process.There is the Different L aFeSiH sample of 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 yalso find out aging fission process in sample, wherein Pr is replaced by some La to increase magnetic calorific intensity.Therefore, aging fission process can occur in RE (TM usually 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) form magneto-caloric material in.In the exemplary embodiment, the value of y can between about 0.8 and 1.5.Alternatively, the y value of different range can be used.As discussed herein, different y values can be used to produce the magneto-caloric material with different Curie temperature.
When magneto-caloric material uses in MR system, the temperature that magneto-caloric material will inevitably be exposed to close to its Curie temperature.In fact, in stratified bed, the material in layer is selected to has the Curie temperature equal with the mean temperature of this layer drawn in MR cycle period.Thus, 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 exceeding 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 the RE (TM when degenerating xsi 1-x) 13h ywhen material is maintained at temperature (such as, 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 finds, as shown in Figure 8, material recovers to carry out quickly at relatively high temperatures.There is the material (i.e. LaFeSiH) of the Curie temperature of 26.7 DEG C by storing the aging division more than a year at such a temperature until as reached 14 DEG C by the magnetic transition width measured by DSC.As being 2.1 DEG C by this initial magnetic transition width measured by DSC.Then the material of degenerating is exposed to as illustrated in the drawing under different temperatures (that is, 38.5 DEG C, 44 DEG C, 60 DEG C and 100 DEG C).At 44 DEG C, expose about 6 days is enough to material to return to its original state completely, and at 60 DEG C, exposes about 3 days be enough to material to return to its original state completely.The reverse being completely enough to obtain aging division less than 1 day is exposed at 100 DEG C.Applicant also finds Pr 0.5la 0.5(Fe 1-xsi x) 13h yaging division to degenerate by this heat treatment be also completely reversibility.As shown in Figure 9, be have also been obtained the recovery of the magnetic transition of the initial point of the LaFeSiH of aging division by the temperature being exposed to reduction, but process is more slowly carried out.LaFeSiH material has the magnetic transition of 1.2 DEG C of width at first, and LaFeSiH material is maintained at close to its curie point of 37 DEG C after 6 days, and magnetic transition is broadened to 4.4 DEG C.By keeping material to be restored at 5 DEG C.Within 100 days, recover afterwards.In the exemplary embodiment, the regeneration temperature being 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 DEG C.
Because aging division degeneration can be fully reversible in a relatively simple manner, so RE (TM xsi 1-x) 13h ymaterial can use in the MR system of suitably changing, and this results in the basis of theme described herein.Have magneto-caloric material stratified bed MR system works normal mode under, material layer will keep close to its respective Curie temperature, and this will cause magneto-caloric material to be deteriorated.In addition, when system does not work, curie point also can be deteriorated close to the magneto-caloric material part of environment temperature.Therefore, applicant has developed a kind of MR system of improvement, any aging division that the MR system of this improvement is configured to keep magneto-caloric material layer can occur with reverse at the temperature being different from magneto-caloric material Curie temperature is degenerated and recovers its whole magnetothermal effect.The temperature that magneto-caloric material is kept can higher or lower than the Curie temperature of magneto-caloric material, and according to required regeneration rate, power system capacity etc., the temperature that magneto-caloric material is kept can differ 10 DEG C, 25 DEG C, 50 DEG C, 100 DEG C etc. with Curie temperature.In the exemplary embodiment, the temperature that magneto-caloric material is kept can differ about 10 DEG C with Curie temperature.
In an illustrative embodiments, MR system uses RE (TMxSi1 -x) 13H yas magneto-caloric material and have access running system in heating element heater.In addition, when MR system is in free time (such as, the residential air conditioner machine at night), heating element heater can be activated.Then MR system makes the fluid be heated cycle through magneto-caloric material, fully reverses any aging division because high-temperature process last time may occur.
Under the particular case of MR system usually absorbing heat at cold heat exchanger (CHEX) place and discharge heat at heat exchanger (HHEX) place, 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 works in a cooling mode, and this refrigeration machine comprises the bed of one or more demagnetization, and these provide cooling to the cold heat exchanger with load thermo-contact to be cooled.One or more magnetized bed discharges heat to heat exchanger.In one embodiment, each bed comprises and has about 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 illustrates the AMR type refrigeration machine worked in recovery mode.In one embodiment, the heater of connecting with multiple heats these and exceeds on 10 DEG C to the most high-Curie-point than the material in these, and these heat exchangers are bypassed.Discuss in more detail as shown in Figure 11 and hereafter, when reforestation practices starts, stream switches to away from cold heat exchanger and stream is redirected heater by valve.When reforestation practices, the second valve can be added to switch stream away from heat exchanger (also seeing Figure 11).These two valves by the isolation of MR system heat, thus use less heater power can be heated the temperature of the curie point about 10 DEG C higher than magneto-caloric materials all in system.If suspend magnet movement or reverse flow of fluids during reforestation practices, AMR cycling is suspended, and it reduces the amount of maintenance heater power required in recovery mode.Because magnet movement and reverse flow of fluids utilize extra electrical power, so suspend these to operate the quantity of power also reducing system in recovery mode and consume.
In alternative embodiment, cooling system is except having heating element heater, and cooling system can also comprise two independently MR subsystems.One MR subsystem can provide the cooling as Figure 10, and the bed of the second subsystem experiences the heat treatment as Figure 11 simultaneously, to reverse aging division.Under these operating conditions after certain time (such as, 1 hour, 2 hours, 4 hours, 12 hours etc.), can switch MR subsystem, the second subsystem provides cooling and the first subsystem experiences 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 its sub-systems experiences heat treatment.
In another alternative embodiment, cooling system can have two sections, and each section comprises the AMR bed of 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 cthe value of 10 DEG C can be had, T mthe value of 25 DEG C can be had, T hthe value of 40 DEG C can be had.At alternative embodiment and/or in implementing, different temperature values can be used.When wanting to recover hot arc magneto-caloric material, cold section can work in a cooling mode, produces temperature close to T ccold outlet fluid stream.This cold fluid does not flow through cold side heat exchanger, but can be directed to by hot arc to obtain close to 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 in a cooling mode and therefore can produce temperature close to T hhot outlet fluid stream.This hot fluid does not flow through hot side heat exchanger, but can be directed to logical super cooled sect to make its temperature close to T h.Because this temperature is far above all Curie temperature in cold section, be exposed to any aging division that this temperature can reverse cold section of material.
In another alternative embodiment, system can comprise two independently MR subsystems, and each subsystem has as two in the above-described embodiment section, i.e. hot arc and cold section.When needs the highest cooling power time, as shown in Figure 12, two subsystems can parallel running, and each subsystem provides cooling.In fig. 12, the section being connected to pump and hot HEX has the LaFeSiH as magneto-caloric material, and its curie point is from T hto T mscope in.The section being 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 the end of the bed being connected to another.As shown in figure 13, when needing less cooling power, under a subsystem may operate in refrigerating mode, and another subsystem may operate under reforestation practices to repair the performance of its magneto-caloric material.In fig. 13, lower subsystem provides cooling power and upper subsystem is in reforestation practices.From the hot arc bed turning to upper subsystem at least partially of the cold outlet fluid stream of the demagnetization bed of lower subsystem.Meanwhile, a part for the hot outlet fluid stream of the magnetizing bed of lower subsystem 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 remaining subsystem experiences heat treatment.At this generally, each subsystem can have two sections as described above.
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 replace with brand-new bed.Can physically away from the isolated system of magnetic refrigerating system, by being exposed to the temperature of the Curie temperature of all layers fully contained away from them, the bed of degeneration can turn back to brand-new state.Such as, this device can be the simple flow circuits with heater, and it can make fluid at high temperature circulate through the bed of degeneration, or this device can be the baking oven making bed keep high temperature.Once return to brand-new state, then these beds can be reinstalled as quickly as possible 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.The computing system of any type known to persons of ordinary skill in the art can be used.In one embodiment, any operation described herein can be changed into by code the instruction be stored on computer-readable medium.Computing system can be utilized to perform these instructions, thus these operations are performed.
Embodiment
In order to verify that aging division is degenerated impact on magnetic refrigerator performance, and in order to verify that high-temperature process is effective for this degeneration of reverse, 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 DEG C, 11 DEG C, 15 DEG C, 18 DEG C and 21 DEG C.Under the operating condition of standard group, test machine, wherein cycle frequency is 3.33Hz, and flow rate is 6 liters/min, and hot inlet temperature is 25 DEG C, and the cooling load provided by electric heater is 400 watts.Before as MR operation, the LaFeSiH in bed is full of by the aqueous fluids of 35 DEG C and reaches 80 hours to make material reach its original state.The temperature span under reference operating condition with the machine of brand-new material is 13.4 DEG C.Then make this machine be in off working state under the environment temperature of 22 DEG C, continue 10 days.In a state in which, Curie temperature is that the material expectation of 18 DEG C and 21 DEG C can be experienced aging division and degenerates, and in fact, the temperature span under reference operating condition of the machine after process in these 10 days drops to only 2.9 DEG C.Then LaFeSiHMCM is full of by the aqueous fluids of 50 DEG C and reaches 19 hours to make material reach its original state, and the temperature span of the machine under AMR pattern under cooling load is 400 watts and hot inlet temperature is the standard conditions of 25 DEG C is through being measured as 13.2 DEG C.Therefore, make LaFeSiHMCM be in than the curie point of material exceed constant temperature 19 on 10 DEG C little time, recover the performance of MCM after the performance that can occur when being remained on by MCM close to its curie point and continue 10 days significantly reduces.
Theme described herein illustrates the different parts comprised in different miscellaneous parts or the different parts connected from different miscellaneous parts sometimes.Should be appreciated that the structure described like this is exemplary, in fact, other structures multiple realizing identical function can be implemented.Concept meaning is considered, any layout realizing the parts of identical function effectively " association " makes to realize required function.Therefore, any two parts combined realizing specific function herein can be regarded as " association " in making each other to realize required function, and have nothing to do with structure or intermediate member.Equally, any two parts of association like this also can be regarded as " being operably connected " or " being operationally coupled " in each other to realize required function, and any two parts that can so associate 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 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 based on context and/or purposes from complex transform to odd number and/or from odd number, transform to plural number.For clarity sake, the conversion of multiple singular/plural is listed herein clearly.
It will be appreciated by those skilled in the art that, in general, term used herein, particularly appending claims (such as, the main body of appended claim) in the term that uses usually be intended to represent the term of " opening " (such as, term " comprises " and being to be understood as " including but not limited to ", and term " has " and is to be understood as " at least having ", term " comprises " 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, then will clearly state in the claims, and when not having this quoting, then do not have such intention.Such as, in order to help to understand, appended claims can comprise the use for introducing introductory phrase " at least one " that claim quotes and " one or more ".But, the use of this phrase does not should be understood to hint, the any specific rights comprising the claim of this introducing requires to be restricted to only to comprise an invention of quoting like this by indefinite article " " or " one ", even when identical claim comprises introductory phrase " one or more " or " at least one " and indefinite article such as "a" or "an" (such as, " one " and/or " one " should be construed as representing " at least one " or " one or more " usually); For the use of the definite article quoted introducing claim, equally so.In addition, even if what list optional network specific digit clearly quotes claim, those skilled in the art will recognize that, this describing is to be understood as at least quoted numeral (such as usually, the basic of " quoting for two " without other modifier describes, ordinary representation at least two is quoted, or two or morely quotes).In addition, when use is similar to the idiom of " in A, B and C etc. at least one ", in general, this structure will understand this idiom (such as, " 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.When use is similar to the idiom of " in A, B or C etc. at least one ", in general, this structure will understand this idiom (such as, " 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 represent two or more substituting term are all to be understood as the possibility giving and comprise one of these terms, these terms any one or two terms.Such as, phrase " A or B " will be understood as that the possibility comprising " A " or " B " or " A and B ".
In order to the purpose of illustration and description, give the above-mentioned explanation of illustrative embodiments.With regard to disclosed clear and definite form, be not intended to exhaustive or restriction, multiple amendment and modification can be made according to above-mentioned instruction or multiple amendment and modification can be obtained from the enforcement of disclosed embodiment.It is noted that scope of the present invention is limited by appending claims and equivalent thereof.

Claims (22)

1., for reversing the method that magneto-caloric material is degenerated, comprising:
Identify at least part of degeneration of the magneto-caloric material in magnetic cooling system, wherein, described magneto-caloric material has Curie temperature; With
By making described magneto-caloric material regenerate under described magneto-caloric material is remained on regeneration temperature, 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 differs at least 5 degrees Celsius with described Curie temperature.
3. the method for claim 1, wherein described regeneration temperature differs at least 10 degrees Celsius with described Curie temperature.
4. the method for claim 1, wherein described magneto-caloric material comprises hydrogen, wherein said regeneration temperature lower than maximum temperature, described maximum temperature be described hydrogen will start temperature when leaving described magneto-caloric material at least partially.
5. the method for claim 1, wherein described magneto-caloric material comprises RE (TM xsi y) 13h z, wherein RE is rare earth element and TM is transition metal.
6. the method for claim 1, also comprises: when keeping described magneto-caloric material under described regeneration temperature, suspends the active magnetic regenerator cycle of described magnetic cooling system.
7. the method for claim 1, also comprises:
Remove described magneto-caloric material from described magnetic cooling system, 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 regenerated.
8. the method for claim 1, wherein regeneration comprises the aging division reversing described magneto-caloric material.
9., for reversing the method that magneto-caloric material is degenerated, comprising:
Form at least one bed of magnetic cooling system, wherein, at least one bed described 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 from described described magneto-caloric material heat transfer at least one;
At least one valve forming described magnetic cooling system flows through at least one bed described and heater or heat exchanger to control described heat-transfer fluid, wherein, described heat-transfer fluid flowing through between described at least one and described heater keeps described magneto-caloric material to regenerate described magneto-caloric material 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 flowing of the described heat-transfer fluid between described at least one and described heat exchanger makes described magneto-caloric material cool.
11. methods as claimed in claim 9, wherein, at least one bed described comprises multiple layer, wherein, at least one each layer described comprises the different magneto-caloric materials with different Curie temperature, wherein, give the described different Curie temperature of the described different magneto-caloric material in given layer during active magnetic regenerator cycle described in the mean temperature of given layer.
12. 1 kinds, for reversing the device that magneto-caloric material is degenerated, comprising:
Heat-transfer fluid;
Bed, described bed comprises the magneto-caloric material with Curie temperature, and wherein, described bed is configured to allow described heat-transfer fluid to transfer heat to described magneto-caloric material or conduct heat from described magneto-caloric material; With
Heater, described heater configuration becomes to keep described magneto-caloric material under regeneration temperature and continues a time quantum, and to regenerate described magneto-caloric material, 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 heat described bed by described heat-transfer fluid.
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 most 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 from described device regenerate for by described heater.
17. 1 kinds of heat transfer systems, comprising:
First subsystem, comprising:
First heat-transfer fluid;
First, described first bed accessory has the first magneto-caloric material, and wherein, described first magneto-caloric material has the first Curie temperature; With
First valve, described first valve configurations becomes to control described first subsystem and works in the regenerative mode or work in a cooling mode; With
Second subsystem, comprising:
Second heat-transfer fluid;
Second, described second bed accessory has the second magneto-caloric material, and wherein, described second magneto-caloric material has the second Curie temperature; With
Second valve, described second valve configurations becomes to control described second subsystem and works in the regenerative mode or work in a cooling mode.
18. heat transfer systems as claimed in claim 17, wherein:
During the first period, described first valve be configured to control described first subsystem work under described refrigerating mode and described second valve be configured to control described second subsystem work under described regeneration mode; With
During the second period, described first valve be configured to control described first subsystem work under described regeneration mode and described second valve be configured to control described second subsystem work under described refrigerating mode.
19. heat transfer systems as claimed in claim 17, wherein, during the given period, described first valve be configured to control described first subsystem work under described refrigerating mode and described second valve be configured to control described second subsystem work 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 first subsystem comprises cold section, makes the different Curie temperature of the described different magneto-caloric material in described 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 second subsystem comprises hot arc, makes the different Curie temperature of the described different magneto-caloric material in described 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 first heat-transfer fluid is in temperature T c, at least one valve in described first valve and described second valve guides at described temperature T cunder described first heat-transfer fluid by described hot arc to regenerate described hot arc.
22. heat transfer systems as claimed in claim 20, wherein, when described hot arc works under described refrigerating mode, described second heat-transfer fluid is in temperature T h, and at least one valve in described first valve and described second valve guides at described temperature T hdescribed second heat-transfer fluid by described cold section to regenerate described cold section.
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