CN110440475A - Anti-oxidant cool storage material and the cold storage Cryo Refrigerator for using the cool storage material - Google Patents
Anti-oxidant cool storage material and the cold storage Cryo Refrigerator for using the cool storage material Download PDFInfo
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- CN110440475A CN110440475A CN201910667502.2A CN201910667502A CN110440475A CN 110440475 A CN110440475 A CN 110440475A CN 201910667502 A CN201910667502 A CN 201910667502A CN 110440475 A CN110440475 A CN 110440475A
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- 239000011232 storage material Substances 0.000 title claims abstract description 128
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 30
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 30
- 235000006708 antioxidants Nutrition 0.000 title claims abstract description 30
- 238000003860 storage Methods 0.000 title claims abstract description 19
- XTPMURFLEDRBCW-UHFFFAOYSA-N bismuth gallium Chemical compound [Ga].[Bi] XTPMURFLEDRBCW-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910000807 Ga alloy Inorganic materials 0.000 claims abstract description 68
- 239000002245 particle Substances 0.000 claims abstract description 56
- 238000005057 refrigeration Methods 0.000 claims abstract description 28
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 14
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 9
- 238000005481 NMR spectroscopy Methods 0.000 claims description 5
- 238000009689 gas atomisation Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 abstract description 7
- 230000003026 anti-oxygenic effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 30
- 239000007789 gas Substances 0.000 description 19
- IYNWNKYVHCVUCJ-UHFFFAOYSA-N bismuth Chemical compound [Bi].[Bi] IYNWNKYVHCVUCJ-UHFFFAOYSA-N 0.000 description 14
- 229910052797 bismuth Inorganic materials 0.000 description 14
- 239000003507 refrigerant Substances 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 235000019589 hardness Nutrition 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- CUQNSZSCQRIWQR-UHFFFAOYSA-N copper holmium Chemical compound [Cu].[Ho] CUQNSZSCQRIWQR-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 230000002792 vascular Effects 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- AGRPPNJBTDEKHA-UHFFFAOYSA-N O.[S-2].[Gd+3] Chemical compound O.[S-2].[Gd+3] AGRPPNJBTDEKHA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- YIAXEFITNBBEOD-UHFFFAOYSA-N gadolinium(3+) trisulfide Chemical compound [S--].[S--].[S--].[Gd+3].[Gd+3] YIAXEFITNBBEOD-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000001681 protective 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
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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
- F25B1/00—Compression machines, plants or systems with non-reversible cycle
- F25B1/02—Compression machines, plants or systems with non-reversible cycle with compressor of reciprocating-piston type
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Devices That Are Associated With Refrigeration Equipment (AREA)
Abstract
The invention discloses a kind of anti-oxidant cool storage material and using the cold storage Cryo Refrigerator of the cool storage material, belong to Cryo Refrigerator technical field, the anti-oxidant cool storage material is bismuth gallium alloy particle, and the mass fraction of the gallium in bismuth gallium alloy particle meets: 0.1% < WGa< 20%.Cold storage Cryo Refrigerator includes regenerator, and the cool storage material filled in the regenerator is bismuth gallium alloy particle.Anti-oxidant cool storage material provided by the present invention is free of lead, anti-oxidant strong, easy nodularization, easily obtains and have preferable hot property, and the refrigeration performance of the anti-oxidant cool storage material is suitable with lead；When so that the anti-oxidant cool storage material being used for regenerative refrigerator, there is preferable heat exchange property；And other cool storage materials are compared, after gallium element is added, enhances the ductility of cool storage material and cool storage material antioxygenic property is enhanced, further improve refrigeration machine performance.
Description
Technical field
The present invention relates to cool storage materials used by Cryo Refrigerator technical field more particularly to low-temperature refrigerant, specifically
It is unleaded, anti-oxidant strong, the easy nodularization of one kind that ground, which is said, easily obtains and has the anti-oxidant cool storage material of preferable hot property and adopt
With the cold storage Cryo Refrigerator of the cool storage material.
Background technique
Regenerative refrigerator is the general designation to the refrigeration machine with regenerator, it may for example comprise GM refrigeration machine, Stirling system
Cold, vascular refrigerator, Sol text refrigeration machine etc..Heat exchange material, referred to as cool storage material are filled in regenerator.As cold-storage
Material, it is necessary to have biggish specific heat capacity under corresponding warm area.The confidential realization of cryogenic refrigeration is imitated from room temperature to the refrigeration of 4K warm area
It answers, it is desirable that the cool storage material specific heat chosen within the scope of corresponding warm area is as big as possible.Same material is in different warm areas and not
It is different in warm area volume specific heat of the same race with material, therefore can be applied to whole warm areas without a kind of material, it is necessary to foundation
Different materials combination is taken in warm area distribution.Warm area from room temperature to 40K, using stainless steel or phosphor bronze silk screen, such as Fig. 1 institute
Show: 40K~10K is using spherical lead (Pb), 10K or less using spherical holmium copper (HoCu2).Lead is opposite in 40K~10K warm area
Other materials has biggish specific heat, cheap to be easily obtained, and is the optimal cool storage material of the warm area.But just environmental protection and
Speech, lead is a kind of heavy metal for being harmful to human body, and to the toxic effect of nerve, animals and plants will appear in various degree after absorbing lead
Poisonous effect.
Summary of the invention
In response to the problems existing in the prior art, the purpose of the present invention is to provide one kind without lead, it is anti-oxidant it is strong, toxicity is low,
Be easy nodularization, it is at low cost, easily obtain and with preferable hot property anti-oxidant cool storage material and using the cool storage material storage
Cold type Cryo Refrigerator.
The purpose of the present invention is what is solved by the following technical programs:
A kind of anti-oxidant cool storage material, it is characterised in that: the anti-oxidant cool storage material is bismuth gallium (Bi-Ga) alloy particle,
And the mass fraction of the gallium in bismuth gallium alloy particle meets: 0.1% < WGa< 20%.
The diameter of the bismuth gallium alloy particle is 0.10mm~1.5mm.
The diameter of the bismuth gallium alloy particle is 0.16mm~1.0mm.
Major diameter accounts for whole bismuth galliums no more than 1.5 bismuth gallium alloy particle to the ratio between minor axis and closes in the bismuth gallium alloy particle
The weight ratio score of gold particle is 80% or more.
The bismuth gallium alloy particle is prepared by the quenching of fusing metal or plasma or gas atomization.
A kind of cold storage Cryo Refrigerator, including regenerator, it is characterised in that: the cool storage material filled in the regenerator
For bismuth gallium alloy particle.
The regenerator includes level-one pushing piston and/or second level pushing piston, one filled in level-one pushing piston
The second level cool storage material filled in grade cool storage material and/or second level pushing piston is using bismuth gallium alloy particle.
When the level-one cool storage material uses bismuth gallium alloy particle, bismuth gallium alloy particle is as level-one pushing piston cold end
Level-one cool storage material.
The second level cool storage material includes second level hot end cool storage material and second level cold end cool storage material, bismuth gallium alloy particle
As the second level hot end cool storage material in second level pushing piston hot end and the second level cold end cool storage material of second level pushing piston cold end is adopted
With GOS or HoCu2。
The second level hot end cool storage material using bismuth gallium alloy particle and second level cold end cool storage material using GOS or
HoCu2When, which is nuclear magnetic resonance 4K Cryo Refrigerator and is applied to superconductive system.
The cold storage Cryo Refrigerator includes Ji Fude-McMahon type refrigeration machine, sterlin refrigerator, Sol text
Refrigeration machine, vascular refrigerator, and do not limit to above-mentioned Cryo Refrigerator, as long as the Cryo Refrigerator with regenerator can fit
With.
The present invention has the following advantages compared with prior art:
Anti-oxidant cool storage material provided by the present invention is free of lead, anti-oxidant strong, easy nodularization, easily obtains and have preferable heat
The refrigeration performance of performance, the anti-oxidant cool storage material is suitable with lead；So that the anti-oxidant cool storage material is used for regenerative refrigerator
When, there is preferable heat exchange property；And other cool storage materials are compared, after gallium element is added, enhances the ductility of cool storage material and make
The enhancing of cool storage material antioxygenic property is obtained, refrigeration machine performance is further improved.
Detailed description of the invention
Attached drawing 1 is the cool storage material distribution schematic diagram loaded in lead regenerator in the prior art；
Attached drawing 2 is the cool storage material distribution schematic diagram loaded in bismuth gallium alloy regenerator of the invention；
Attached drawing 3 is the structural schematic diagram of the ultra-low temperature refrigerating device of one embodiment of the present invention；
Attached drawing 4 is the structural section figure of the second level pushing piston in GM refrigeration machine involved in embodiments of the present invention；
Attached drawing 5 is the volume ratio heating curve figure of different cool storage materials according to the present invention；
Attached drawing 6 is material bismuth and bismuth gallium alloy oxidation rate comparison diagram；
The size and the refrigerating capacity curve graph under second level cryogenic temperature 4.2K that attached drawing 7 is bismuth gallium alloy particle；
Attached drawing 8 is the performance comparison figure of bismuth gallium alloy particle cool storage material and lead regenerative materials of the invention；
Attached drawing 9 is Cryo Refrigerator 150h short-term stability performance test figure of the invention.
Wherein: 1-compressor；2-cover components；3-gas pipings；7-sealing rings；8-hot chambers；9-one-stage expansions
Chamber；10-compound expansion chambers；11-level-one pushing pistons；The preceding hole of 11a-first stage piston；11b-first stage piston metapore；11c—
Level-one cool storage material；12-second level pushing pistons；The preceding hole of 12a-second piston；12b-exhaust outlet；12c-second level coolness storing material
Material；12c1-second level hot end cool storage material；12c2-second level cold end cool storage material；12d-second piston cylinder；13-cylinders；
13b-secondary heat exchanger；30-partition members；GOS-oxygen gadolinium sulfide (Gd2O2S)；HoCu2- holmium copper；Pb-lead；Bi-bismuth；
Ga-gallium.
Specific embodiment
The present invention will be further described below with reference to the accompanying drawings and embodiments.
A kind of anti-oxidant cool storage material, the anti-oxidant cool storage material are bismuth gallium alloy particle, the gallium in bismuth gallium alloy particle
Mass fraction meet: 0.1% < WGa< 20%；And bismuth gallium alloy particle is the granule that diameter is 0.10mm~1.5mm, bismuth
Bismuth gallium alloy particle of the major diameter to the ratio between minor axis no more than 1.5 accounts for the weight ratio of whole bismuth gallium alloy particles in gallium alloy particle
Score is 80% or more.Above-mentioned bismuth gallium alloy particle passes through the quenching of fusing metal or plasma or gas atomization system
It is standby to form.
It is as in Figure 2-4: a kind of cold storage Cryo Refrigerator, including regenerator, the interior cool storage material filled of the regenerator
For bismuth gallium alloy particle.Above-mentioned regenerator includes level-one pushing piston 11 and/or second level pushing piston 12, the level-one passage
The second level cool storage material 12c filled in the level-one cool storage material 11c and/or second level pushing piston 12 filled in piston 11 uses bismuth
Gallium alloy particle.When level-one cool storage material 11c uses bismuth gallium alloy particle, bismuth gallium alloy particle is as level-one pushing piston 11
The level-one cool storage material 11c of cold end；Second level cool storage material 12c includes second level hot end cool storage material 12c1 and second level cold end coolness storing material
Expect 12c2, second level hot end cool storage material 12c1 and second level pushing piston of the bismuth gallium alloy particle as 12 hot end of second level pushing piston
The second level cold end cool storage material 12c2 of 12 cold ends uses GOS or HoCu2.It is further to note that second level hot end coolness storing material
Expect that 12c1 uses GOS or HoCu using bismuth gallium alloy particle and second level cold end cool storage material 12c22When, the cold storage low temperature system
Cold is nuclear magnetic resonance 4K Cryo Refrigerator and is applied to superconductive system.
As shown in Figure 3: Fig. 3 is the structural schematic diagram of the Cryo Refrigerator of one embodiment of the present of invention.Refrigeration machine includes
Compressor 1, cover component 2, gas piping 3, cylinder 13, level-one pushing piston 11, second level pushing piston 12, compressor 1 pass through
It by refrigerant gas sucking, compression, and is allowed to be discharged as the refrigerant gas of high pressure, gas piping 3 is by the refrigeration of the high pressure
Agent gas is supplied to cover component 2；Cylinder 13 is the cylinder of two-stage type, and ontology is made of 304 stainless steels, two-stage cylinder
It is coaxially arranged.Level-one pushing piston 11 and second level pushing piston 12 are coaxially connected, in the drive of driving mechanism (being not drawn into figure)
Under moved in cylinder 13 along the direction Z1~Z2 together, level-one pushing piston 11 and second level pushing piston 12 top into figure
(direction Z1) is mobile, then the volume of one-stage expansion chamber 9 and compound expansion chamber 10 increases.Conversely, corresponding expansion chamber volume becomes smaller.
Under the variation of above-mentioned expansion chamber volume, the refrigerant gas of incoming flow is pushed away by the preceding hole 11a of first stage piston with level-one
The level-one cool storage material 11c moved inside piston 11 carries out heat exchange, then flows out from first stage piston metapore 11b；A part of gas exists
It is expanded in one-stage expansion chamber 9, remaining gas is flowed into second level pushing piston 12 by the preceding hole 12a of second piston, with it
Internal second level cool storage material 12c exchanges heat, and then flows out, enters in compound expansion chamber 10, the process from exhaust outlet 12b
For refrigerant gas by the heat transfer of itself to cool storage material, temperature becomes low temperature by room temperature.Along above-mentioned gas flow direction,
That is the direction Z2, cylinder 13 and level-one pushing piston 11, second level pushing piston 12 continuously reduce, formation temperature gradient.
The gas of reflux and above-mentioned flow process are on the contrary, refrigerant gas passes through exhaust outlet from the outflow of compound expansion chamber 10
12b exchanges heat with the second level cool storage material 12c in second level pushing piston 12, swollen with level-one from the preceding hole 12a outflow of second piston
Refrigerant gas mixing in swollen chamber 9；Then pass through first stage piston metapore 11b, with the level-one cold-storage in level-one pushing piston 11
Material 11c exchanges heat, and then by the preceding hole 11a of first stage piston, enters in cover component 2, then flows into the low pressure of compressor 1
Side.The process refrigerant gas absorbs heat from cool storage material, becomes room temperature by low temperature.
By the way that above movement, level-one cool storage material 11c, second level cool storage material 12c and refrigerant gas quilt is repeated
It is cooling.Cryogenic gas continuous expansion work in one-stage expansion chamber 9 and compound expansion chamber 10 forms refrigeration source.
It is described in detail by taking the second level cool storage material 12c in second level pushing piston 12 as an example below.
As shown in figure 4, according to the difference of warm area, second level cool storage material 12c generally divides in order to promote refrigeration machine cooling effect
It is divided into two parts: second level hot end cool storage material 12c1 and second level cold end cool storage material 12c2, and be contained in regenerator (second level pushes away
Move piston 12) in.There are the preceding hole 12a of second piston, lower part to have exhaust outlet 12b and second level on the top of second level pushing piston 12
Cool storage material 12c forms porous channel, porous channel and exhaust outlet in the preceding hole 12a of second piston, second level cool storage material 12c
12b forms the gas passage of perforation.Three pieces of partition members 30 are installed in second level pushing piston 12, by second level hot end coolness storing material
Material 12c1 and second level cold end cool storage material 12c2 is firmly fixed therein portion；Partition member 30 allows refrigerant gas to flow through,
But does not allow cool storage material to pass through, therefore second level hot end cool storage material 12c1 and second level cold end storage can be designed according to different warm areas
Cold material 12c2.
Specifically: after 2002, the cool storage material of 4.2K warm area obtains tremendous expansion, second level cold end cool storage material 12c2
Generally use HoCu2Either HoCu2And GOS(Gd2O2S/ oxygen gadolinium sulfide) combination because under the warm area, cool storage material
HoCu2There is biggish specific heat with respect to other cool storage materials with GOS, Cryo Refrigerator has biggish refrigeration effect, and refrigerating capacity exists
4.2K can reach 1W, and can use in magnetic field, is not in decaying, has become the coolness storing material of 4K Cryo Refrigerator standard configuration
Material, is widely used in NMR system, is used for cooling superconducting magnets.
When the specific heat peak value due to GOS is in 5.2K, after temperature is greater than 5.2K, specific heat can be strongly reduced；Additionally, due to HoCu2
It is expensive for rare-earth metal material, therefore the cool storage material in entire second level pushing piston 12 all loads HoCu2And GOS
Without economy and feasibility.The alloy of conventionally employed lead (Pb) either lead, not only specific heat is big, good effect of heat exchange and valence
Lattice are cheap, are easy to obtain.But lead is as heavy metal element, all toxic to human body, animals and plants, the whole world was since 2006
Through strictly being managed to lead.
The comparison of the volumetric specific heat capacity of each material as shown in Figure 5 proposes to use a kind of bismuth gallium alloy grain in the present invention
Son is used as cool storage material, is able to solve the above problem.Bismuth ball is crisp and hard, lacks ductility, is easy to produce under the impact of high pressure
Powder, and easy to oxidize in the specific implementation process, the heat transfer being unfavorable between helium, cause refrigeration machine second level refrigeration performance
Decline.Therefore gallium element is added in bismuth, forms bismuth gallium alloy.It is advantageous in that the ductility of enhancing cool storage material, convenient for manufacturing,
Reduce cost；Gallium element has anti-oxidation function simultaneously, can prevent cool storage material from aoxidizing, and improves the refrigerator operation service life.
Anti-oxidant experiment further is carried out to material bismuth and bismuth gallium alloy, slag is periodically scraped, isolates oxide therein,
The degree of oxidation of material is indicated with the weight of oxide.Fig. 6 illustrates the weight of 24 hours oxides of material bismuth and bismuth gallium alloy
Amount, in 24 hours, the oxidation rate of bismuth is 4.9 times of bismuth gallium alloy oxidation rate, i.e. the inoxidizability of bismuth gallium alloy is anti-for bismuth
4.9 times of oxidisability.Sample surfaces are analyzed using power spectrum view, it is found that bismuth and bismuth gallium surface power spectrum have very big difference.Gallium
Element is highly enriched in surface, so that the content of bismuth on the surface of the material is greatly lowered, forms the superficial layer that unique rich gallium lacks bismuth.
Gallium element is forming fine and close protective film on the surface of the material, prevents the further oxidation of material, and what material bismuth surface was formed
Film unprotect, over time, oxidation film continuously thickens.Testing surface, bismuth gallium alloy can be kept for consecutive numbers ten hours
Bright color, and material bismuth gradually graying black, lose original bright color.Gallium element is added, the oxygen of material is effectively inhibited
Change.Bismuth gallium alloy has stronger inoxidizability.
In the implementation process, the hardness and density of cool storage material are as shown in table 1.
| Title material | HoCu2 | Pb | Bi-Ga |
| Vickers hardness | 327 | 11.8 | 12.5 |
| Density (g/cm3) | 8.89 | 11.34 | 9.5 |
The different cool storage material Vickers hardnesses of table 1 and density contrast table
As shown in table 1, in terms of hardness, selected bismuth gallium alloy particle have with the comparable hardness of lead, and carry out repeated stock
Do not find that fracture phenomena occurs in particle during test.It is less than lead additionally, due to bismuth gallium alloy density, therefore under equal volume
Dosage is smaller, and economy is more preferable, conducive to the cost for reducing Cryo Refrigerator.
Fig. 7 illustrates the pass of the size (particle diameter) and refrigerating capacity under second level cryogenic temperature 4.2K of bismuth gallium alloy particle
System, the diameter of the bismuth gallium alloy particle for 4K~10K Cryo Refrigerator reliably meet refrigeration machine between 0.1~1.5mm
It can demand.It further illustrates, the diameter of bismuth gallium alloy particle is more preferably to select between 0.16~1mm.
In the present invention, lead and bismuth gallium alloy particle are carried out to the comparative test of second level hot end cool storage material 12c1, are based on
1.5W 4.2K Cryo Refrigerator, the performance of bismuth gallium alloy cool storage material is evaluated.As shown in figure 8, holmium copper loading is protected
Consistent, bismuth gallium alloy cool storage material and lead regenerative materials performance comparison figure are held, wherein control level-one cryogenic temperature is 50K.From Fig. 8
It can be found that bismuth gallium alloy makees second level hot end cool storage material and lead makees second level hot end cool storage material, refrigeration-grade second level cryogenic temperature
Refrigeration performance having the same under 4.2K.
Bismuth gallium alloy cool storage material progress stability is examined in addition, the present invention also passes through short-term stability test in 150 hours
It examines, as shown in Figure 9.During the test, regenerator experienced cooling thermal impact repeatedly, by checking bismuth gallium alloy cool storage material,
Do not occur rupture, go out powder phenomenon, this shows that bismuth gallium alloy is a kind of cool storage material that can be used for Cryo Refrigerator.
In embodiments of the invention, the holmium that the second level cold end cool storage material 12c2 of 12 cold end of second level pushing piston is used
Copper can also use holmium copper and GOS combination to promote refrigeration machine performance.
As described above, the second level in embodiment of the present invention, using bismuth gallium alloy particle as regenerative refrigerator
Fusing metal quenching method can be used in the second level hot end cool storage material 12c1 of pushing piston 12, second level hot end cool storage material 12c1
Either plasma or gas atomization method are made.
The regenerator that cool storage material of the invention is loaded is that the second level of twin-stage Cryo Refrigerator in embodiment elapses work
Plug 12 has bismuth gallium alloy cool storage material particle provided by the present invention as shown in Figure 2,4.Meanwhile storage provided by the present invention
Cold type Cryo Refrigerator has Low temperature regenerator of the filling bismuth gallium alloy particle as second level hot end cool storage material 12c1；And it can be with
Holmium copper, GOS combination are used for nuclear magnetic resonance 4K Cryo Refrigerator, are used for cooling superconducting magnets.
In embodiments above, cool storage material provided by the invention be suitable for Ji Fude-McMahon type refrigeration machine, this
Special woods refrigeration machine, Sol text refrigeration machine, vascular refrigerator, and do not limit to above-mentioned Cryo Refrigerator, as long as with regenerator
Cryo Refrigerator is applicable.
Cool storage material provided by the present invention is free of lead, anti-oxidant strong, easy nodularization, easily obtains and have compared with thermophilic
Can, the refrigeration performance of the cool storage material is suitable with lead；When so that the cool storage material being used for regenerative refrigerator, there is preferable heat exchange
Performance；And other cool storage materials are compared, after gallium element is added, enhances the ductility of cool storage material and make cool storage material anti-oxidant
Performance is strong, further improves refrigeration machine performance.
The above examples only illustrate the technical idea of the present invention, and this does not limit the scope of protection of the present invention, all
According to the technical idea provided by the invention, any changes made on the basis of the technical scheme each falls within the scope of the present invention
Within；The technology that the present invention is not directed to can be realized by the prior art.
Claims (10)
1. a kind of anti-oxidant cool storage material, it is characterised in that: the anti-oxidant cool storage material is bismuth gallium alloy particle, and bismuth gallium
The mass fraction of gallium in alloy particle meets: 0.1% < WGa< 20%.
2. anti-oxidant cool storage material according to claim 1, it is characterised in that: the diameter of the bismuth gallium alloy particle is
0.10mm~1.5mm.
3. anti-oxidant cool storage material according to claim 2, it is characterised in that: the diameter of the bismuth gallium alloy particle is
0.16mm~1.0mm.
4. anti-oxidant cool storage material according to claim 1, it is characterised in that: major diameter pair in the bismuth gallium alloy particle
The weight ratio score that bismuth gallium alloy particle of the ratio between the minor axis no more than 1.5 accounts for whole bismuth gallium alloy particles is 80% or more.
5. anti-oxidant cool storage material according to claim 1, it is characterised in that: the bismuth gallium alloy particle passes through fusing
Metal quenching or plasma or gas atomization are prepared.
6. a kind of cold storage Cryo Refrigerator using anti-oxidant cool storage material a method as claimed in any one of claims 1 to 5, including store
Cooler, it is characterised in that: the cool storage material filled in the regenerator is bismuth gallium alloy particle.
7. cold storage Cryo Refrigerator according to claim 6, it is characterised in that: the regenerator includes level-one passage
Piston (11) and/or second level pushing piston (12), the level-one cool storage material (11c) filled in level-one pushing piston (11) and/or
The second level cool storage material (12c) filled in second level pushing piston (12) uses bismuth gallium alloy particle.
8. cold storage Cryo Refrigerator according to claim 7, it is characterised in that: the level-one cool storage material (11c)
When using bismuth gallium alloy particle, level-one cool storage material (11c) of the bismuth gallium alloy particle as level-one pushing piston (11) cold end.
9. cold storage Cryo Refrigerator according to claim 7, it is characterised in that: the second level cool storage material (12c)
Including second level hot end cool storage material (12c1) and second level cold end cool storage material (12c2), bismuth gallium alloy particle is elapsed as second level and is lived
Fill in the second level hot end cool storage material (12c1) in (12) hot end and the second level cold end cool storage material of second level pushing piston (12) cold end
(12c2) uses GOS or HoCu2。
10. cold storage Cryo Refrigerator according to claim 9, it is characterised in that: the second level hot end cool storage material
(12c1) uses GOS or HoCu using bismuth gallium alloy particle and second level cold end cool storage material (12c2)2When, the cold storage low temperature
Refrigeration machine is nuclear magnetic resonance 4K Cryo Refrigerator and is applied to superconductive system.
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| CN201910667502.2A CN110440475A (en) | 2019-07-23 | 2019-07-23 | Anti-oxidant cool storage material and the cold storage Cryo Refrigerator for using the cool storage material |
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| CN201910667502.2A CN110440475A (en) | 2019-07-23 | 2019-07-23 | Anti-oxidant cool storage material and the cold storage Cryo Refrigerator for using the cool storage material |
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Application publication date: 20191112 |