CN103773995A - Magnetic cool storage material - Google Patents
Magnetic cool storage material Download PDFInfo
- Publication number
- CN103773995A CN103773995A CN201410049549.XA CN201410049549A CN103773995A CN 103773995 A CN103773995 A CN 103773995A CN 201410049549 A CN201410049549 A CN 201410049549A CN 103773995 A CN103773995 A CN 103773995A
- Authority
- CN
- China
- Prior art keywords
- storage material
- magnetic cold
- specific heat
- hocu
- cold
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 239000011232 storage material Substances 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000000889 atomisation Methods 0.000 claims abstract description 4
- 239000012798 spherical particle Substances 0.000 claims abstract description 4
- 238000005266 casting Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 230000006698 induction Effects 0.000 claims description 9
- 238000000137 annealing Methods 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 abstract 1
- 239000000155 melt Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000010949 copper Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a HoCu[2-x]Nix series magnetic cool storage material for a cryo refrigerator. The magnetic cool storage material has larger volumetric specific heat in 10-40K temperature area, has larger width of specific heat peak, and can substitute for Pb to be used as the cool storage material for 10-40K temperature area. The HoCu[2-x]Nix series magnetic cool storage material has the outstanding characteristics that the position and the specific heat peak value can be regulated by controlling the content of Ni, when the additive proportion x of Ni is equal to 0.4, the material has specific heat peak at 20.2K, and the specific heat peak value is 0.95J/cm<3>K. According to the HoCu[2-x]Nix series magnetic cool storage material, the cast ingot can be directly manufactured into particle materials for use by a mechanical crushing method, or can be manufactured into spherical particle materials for use by a melt atomization method or a rotation electrode method, and 0.154-0.30mm spherical particle is in the best use form.
Description
Technical field
The present invention relates to a kind of magnetic cold-storage material used for cryogenic refrigerator, the Specific Heat Capacity of this series magnetic cold-storage material is adjustable in 10K ~ 40K warm area, can use as cool storage material by alternative metals Pb.
Background technology
Along with scientific and technical develop rapidly, various demands small-sized, high efficient cryogenic refrigerator are increased day by day.Wherein, the small-sized cold storage Gas Refrigerator using helium as working medium, obtains widespread use with its dependable performance, the feature such as simple in structure in various sophisticated technologies field.For small-sized cold storage Gas Refrigerator, regenerator is its key part, and the quality of cool storage material performance has a direct impact for the performance tool of refrigerator, its final decision refrigerating efficiency and the lowest refrigerating temperature that may reach.
Lead is the material (θ that in many metals, debye temperature is lower
d=102K), its lattice specific heat is larger, thereby, in refrigerator, be widely used as 10 ~ 40K warm area low-temperature cold accumulation material.But, the low-temperature region below 15K, plumbous specific heat sharply reduces along with the reduction of temperature, and the efficiency of regenerator is reduced greatly.Warm area below 10K, the specific heat of Pb is no longer greater than the specific heat of refrigeration working medium helium, and there is thermal saturation phenomenon in regenerator, makes the efficiency of refrigerator almost nil below 8K.In addition, European Union starts formal enforcement " in electric, electronics, restriction is used some objectionable impurities instruction " (being called for short " ROHS " instruction) on July 1st, 2006, the use of restriction plumbous (Pb), therefore, find novel high-performance equivalent material and become the important directions of low-temperature cold accumulation investigation of materials.
There is magnetic phase transition at low-temperature region in some rare-earth magnetic compound, externally shows very large magnetic specific heat capacity, thereby make the overall specific heat capacity of material present abnormal increase phenomenon.Research shows, the low-temperature region below 15K, and the magnetic specific heat capacity peak value that magnetic phase transition occurs often holds large one more than the order of magnitude than lattice specific heat, replaces Pb and becomes possibility as cool storage material thereby make to find novel substance.Warm area below 10K, can replace lead to mainly contain as the magnetic substance of cool storage material: HoCu
2, Er
3ni, ErNi, ErNi
2, Er
1-xdy
xni
2, Er (Ni
11-xco
x)
2, Er
1-xyb
xni, Er
l-xho
xni
2, Er
xdy
l-xsb, RNiGe (R=Gd, Dy, Er), Gd
2o
2s, GdAlO
3deng.Wherein, HoCu
2because there is large specific heat capacity and become the low-temperature cold accumulation material being most widely used at present in 10 K at 4 K.
But the research that substitutes cool storage material Pb about the above warm area of 10K is few, therefore, the present invention has prepared HoCu
2-xni
xseries magnetic cold-storage material, has obtained good Specific Heat Capacity at the above warm area of 10K, can be used as the equivalent material of 10 ~ 40 K warm area Pb.
Summary of the invention
The object of the present invention is to provide the HoCu in 10 ~ 40K warm area with large specific heat
2-xni
xseries magnetic cold-storage material, applies on Cryo Refrigerator to substitute conventional cool storage material Pb.
In order to realize object of the present invention, following technical scheme is proposed:
A kind of magnetic cold-storage material, described magnetic cold-storage material is the HoCu that Ho, Ni, tri-kinds of elements of Cu form
2-xni
xseries, wherein x=0.01 ~ 1.99; Described HoCu
2-xni
xthe magnetic cold-storage material of series has high Specific Heat Capacity in 10 ~ 40K warm area, and Specific Heat Capacity is adjusted by the ratio that changes Ni element.
Described magnetic cold-storage material can adopt induction heating or non-consumable arc furnace melting.
Described magnetic cold-storage material, in the time of Ni content x<0.8, directly uses with as cast condition; In Ni content x >=0.8 o'clock, material is carried out to homogenizing annealing processing, annealing region is 800 ~ 900 ℃, soaking time is 12 ~ 48h, further improves the homogeneity of material structure, performance.
Described magnetic cold-storage material adopts mechanical crushing method directly ingot casting to be processed into granulate material and uses.
Described magnetic cold-storage material can adopt melt atomization or rotating electrode method to be processed into form of spherical particles materials'use.
Preferable particle size when described granulate material uses in regenerator is 0.154 ~ 0.30mm.
The present invention has prepared HoCu
2-xni
xseries magnetic cold-storage material, this magnetic cold-storage material has larger volume specific heat in 10-40K warm area, its transformation temperature and Specific Heat Capacity are adjustable in 10 ~ 40K warm area, have higher than thermal peak, cover the feature of wide temperature region than thermal spike, than the equal capable of regulating of the height of thermal spike and position, can substituted metal Pb, use and have application prospect as 10～40K warm area cool storage material.
Accompanying drawing explanation
Fig. 1 is HoCu
2-xni
xthe XRD diffractogram of series alloy.As seen from the figure, Ho (Cu
1-xni
x)
2series alloy keeps good phase structure.
Fig. 2 is HoCu
2-xni
xthe ratio heating curve of series alloy, as seen from the figure, alternative the making of Ni moved to high-temperature zone than thermal peak, increase, and covering warm area broadens than thermal peak.
Embodiment
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with the drawings and specific embodiments, the present invention is described in more detail.
Metal Pb is due to poisonous and be restricted in the application on refrigerator, therefore, find novel high-performance substitute cool storage material become imperative.The specific heat unusual phenomenon of bringing out based on magnetic phase transition, making to explore Novel cold-storage material becomes possibility.HoCu
2show large specific heat capacity at 4 ~ 10K warm area, and at the above warm area of 10K than the rapid attenuating of thermal characteristics, this limited its in the application of higher temperatures district may.
The present invention adopts by adding alloying element Ni to replace Cu, preparation HoCu
2-xni
xseries material, by adjusting the add-on of Ni element, realizes material magnetic heating performance adjustable at 10 ~ 40K warm area, has obtained good effect.
HoCu of the present invention
2-xni
xseries material adopts metal holmium, copper and nickel as starting material, stoicheiometry is formulated according to the rules, can adopt induction heating or non-consumable arc furnace melting, water cooled copper mould casting, ingot casting can further be processed into required shape for refrigerator according to actual requirement.
HoCu of the present invention
2-xni
xthe use form of series material on refrigerator is particulate state, specifically can adopt mechanical crushing method to be prepared into irregular particle, or adopts melt atomization to be prepared into spheroidal particle.In order to increase packing ratio, the optimization size range of particle size is 0.154 ~ 0.3mm.
Embodiment 1:
Stoicheiometry preparation HoCu according to the rules
1.9ni
0.1, adopt Medium Frequency Induction Heating Furnace melting to prepare ingot casting, then adopt centrifugal atomizing apparatus processing globulate particle.
Embodiment 2:
Stoicheiometry preparation HoCu according to the rules
1.7ni
0.3, adopt Medium Frequency Induction Heating Furnace melting to prepare ingot casting, then adopt rotating electrode method to be prepared into spheroidal particle.
Embodiment 3:
Stoicheiometry preparation HoCu according to the rules
1.5ni
0.5, adopt Medium Frequency Induction Heating Furnace melting to prepare ingot casting, direct mechanical is broken into particle, and wherein 0.154 ~ 0.3mm sized particles of screening, can directly be used as regenerator filler.
Embodiment 4:
Stoicheiometry preparation HoCu according to the rules
1.4ni
0.6, adopt Medium Frequency Induction Heating Furnace melting to prepare ingot casting, then adopt centrifugal atomizing apparatus processing globulate particle.
Embodiment 5:
Stoicheiometry preparation HoCu according to the rules
1.2ni
0.8, adopt Medium Frequency Induction Heating Furnace melting to prepare ingot casting, then adopt centrifugal atomizing apparatus processing globulate particle, then by particle under the protection of Ar gas in 800 ℃ × 48 hours homogenizing annealings, can be used for regenerator filler.
Embodiment 6:
Stoicheiometry preparation HoCu according to the rules
1.0ni
1.0, adopt Medium Frequency Induction Heating Furnace melting to prepare ingot casting, then adopt centrifugal atomizing apparatus processing globulate particle, screening wherein 0.154 ~ 0.3mm sized particles under the protection of Ar gas in 850 ℃ × 36 hours homogenizing annealings, can be used for regenerator filler.
Implementation result example
Implementation result example 1:
Stoicheiometry preparation HoCu according to the rules
1.8ni
0.2, adopting non-consumable arc furnace melting, ingot casting was through 800 ℃ × 48 hours homogenizing annealings, and as shown in Figure 1, Specific Heat Capacity as shown in Figure 2, at 10.6K, is 0.53J/cm than thermal peak to sample phase structure
3k.
Implementation result example 2:
Stoicheiometry preparation HoCu according to the rules
1.6ni
0.4, adopting non-consumable arc furnace melting, ingot casting was through 800 ℃ × 48 hours homogenizing annealings, and as shown in Figure 1, Specific Heat Capacity as shown in Figure 2, at 20.2K, is 0.95J/cm than thermal peak to sample phase structure
3k.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect have been carried out to further detailed description; institute is understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (6)
1. a magnetic cold-storage material, is characterized in that: described magnetic cold-storage material is the HoCu that Ho, Ni, tri-kinds of elements of Cu form
2-xni
xseries, wherein x=0.01 ~ 1.99; Described HoCu
2-xni
xthe magnetic cold-storage material of series has high Specific Heat Capacity in 10 ~ 40K warm area, and Specific Heat Capacity is adjusted by the ratio that changes Ni element.
2. magnetic cold-storage material claimed in claim 1, is characterized in that: described magnetic cold-storage material can adopt induction heating or non-consumable arc furnace melting.
3. magnetic cold-storage material claimed in claim 2, is characterized in that: described magnetic cold-storage material, in the time of Ni content x<0.8, directly uses with as cast condition; In Ni content x >=0.8 o'clock, material is carried out to homogenizing annealing processing, annealing region is 800 ~ 900 ℃, soaking time is 12 ~ 48h, further improves the homogeneity of material structure, performance.
4. magnetic cold-storage material claimed in claim 3, is characterized in that: described magnetic cold-storage material adopts mechanical crushing method directly ingot casting to be processed into granulate material and uses.
5. magnetic cold-storage material claimed in claim 3, is characterized in that: described magnetic cold-storage material can adopt melt atomization or rotating electrode method to be processed into form of spherical particles materials'use.
6. the magnetic cold-storage material described in claim 4 or 5, is characterized in that: preferable particle size when described granulate material uses in regenerator is 0.154 ~ 0.30mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410049549.XA CN103773995B (en) | 2014-02-13 | 2014-02-13 | A kind of magnetic cold-storage material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410049549.XA CN103773995B (en) | 2014-02-13 | 2014-02-13 | A kind of magnetic cold-storage material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103773995A true CN103773995A (en) | 2014-05-07 |
| CN103773995B CN103773995B (en) | 2017-09-15 |
Family
ID=50566748
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105063450A (en) * | 2015-07-24 | 2015-11-18 | 北京科技大学 | High-intensity large-specific heat multiphase magnetic cold accumulation material and preparation method thereof |
| WO2018199278A1 (en) * | 2017-04-28 | 2018-11-01 | 株式会社三徳 | Hocu-based cold-storage material, and cold-storage device and refrigerating machine each equipped therewith |
| CN113265552A (en) * | 2021-04-30 | 2021-08-17 | 福建省长汀金龙稀土有限公司 | Preparation method of rare earth holmium copper alloy for magnetic refrigeration |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1248319A (en) * | 1997-10-20 | 2000-03-22 | 株式会社东芝 | Cold-accumulating material and cold-accumulating refrigerator |
| CN101168448A (en) * | 2007-08-16 | 2008-04-30 | 北京科技大学 | Low-temperature large specific heat magnetic cold-storage material preparation method thereof |
-
2014
- 2014-02-13 CN CN201410049549.XA patent/CN103773995B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1248319A (en) * | 1997-10-20 | 2000-03-22 | 株式会社东芝 | Cold-accumulating material and cold-accumulating refrigerator |
| CN101168448A (en) * | 2007-08-16 | 2008-04-30 | 北京科技大学 | Low-temperature large specific heat magnetic cold-storage material preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105063450A (en) * | 2015-07-24 | 2015-11-18 | 北京科技大学 | High-intensity large-specific heat multiphase magnetic cold accumulation material and preparation method thereof |
| CN105063450B (en) * | 2015-07-24 | 2017-06-20 | 北京科技大学 | Big specific heat multiphase magnetic cold-storage material of high intensity and preparation method thereof |
| WO2018199278A1 (en) * | 2017-04-28 | 2018-11-01 | 株式会社三徳 | Hocu-based cold-storage material, and cold-storage device and refrigerating machine each equipped therewith |
| JP6495546B1 (en) * | 2017-04-28 | 2019-04-03 | 株式会社三徳 | HoCu-based regenerator material and regenerator and refrigerator equipped with the same |
| CN110546234A (en) * | 2017-04-28 | 2019-12-06 | 株式会社三德 | HoCu-based regenerative material, and regenerator and refrigerator provided with same |
| EP3617288A4 (en) * | 2017-04-28 | 2020-12-09 | Santoku Corporation | Hocu-based cold-storage material, and cold-storage device and refrigerating machine each equipped therewith |
| US11370949B2 (en) | 2017-04-28 | 2022-06-28 | Santoku Corporation | HoCu-based cold-storage material, and cold-storage device and refrigerating machine each equipped therewith |
| CN113265552A (en) * | 2021-04-30 | 2021-08-17 | 福建省长汀金龙稀土有限公司 | Preparation method of rare earth holmium copper alloy for magnetic refrigeration |
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| Publication number | Publication date |
|---|---|
| CN103773995B (en) | 2017-09-15 |
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