CN103031501B - Erbium base amorphous composite magnetic cold-storage material and preparation method thereof, Cryo Refrigerator - Google Patents
Erbium base amorphous composite magnetic cold-storage material and preparation method thereof, Cryo Refrigerator Download PDFInfo
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- CN103031501B CN103031501B CN201110300107.4A CN201110300107A CN103031501B CN 103031501 B CN103031501 B CN 103031501B CN 201110300107 A CN201110300107 A CN 201110300107A CN 103031501 B CN103031501 B CN 103031501B
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Abstract
The present invention relates to a kind of erbium base amorphous composite magnetic cold-storage material, this alloy is main component with erbium, at Er
3ni and Er
3formulated on the component base of Co, its composition can be formulated as: (Er
0.75t
0.25)
aal
bx
c.The invention still further relates to the preparation method of this erbium base amorphous composite magnetic cold-storage material, and comprise the Cryo Refrigerator of this erbium base amorphous composite magnetic cold-storage material.Erbium base amorphous compound cryosar magnetic cold-storage material of the present invention has: preparation method is simple, Heat stability is good, the processing treatment ability that resistance of oxidation is strong and supercooling liquid phase region is superior, and the position of specific heat peak value and width such as can to regulate at the feature, thus have potential application prospect as low temperature magnetic cool storage material.
Description
Technical field
The present invention relates to low-temperature physics and material science, relate to a kind of erbium base amorphous composite magnetic cold-storage material and preparation method specifically, and comprise the Cryo Refrigerator of this erbium base amorphous composite magnetic cold-storage material.
Background technology
Low-temperature refrigeration technology, as the important branch of low temperature technique, has been widely used in the numerous areas such as meteorology, military affairs, aerospace, cryotronics, hypothermal medicine.High efficiency Cryo Refrigerator has wide application prospect at industrial circle, is subject to extensive concern.At the low temperature lower than 15K, the refrigerating efficiency of Cryo Refrigerator depends primarily on the efficiency of its regenerator.The regenerator of Cryo Refrigerator is a kind of energy-storing device efficiently, and the cool storage material with high heat capacity is stored respectively and releases energy in the compression and expansion process of refrigeration cycle, carries out heat exchange with working fluid.Therefore, the key property of low-temperature cold accumulation material should have large unit volume specific heat under its working temperature.But in normal circumstances, the specific heat of solid matter results from the thermal vibration of Lattice System, and along with the reduction of temperature, the thermal vibration of lattice is more and more weak, and the specific heat of solid is also more and more lower.Such as, plumbous specific heat is 0.35J/Kcm when 15K
3, when dropping to 4K, only have 0.009J/Kcm
3, so low specific heat makes the output cold of cold-storage machine when low temperature be approximately zero, seriously have impact on the efficiency of refrigerator.Except lattice specific heat and the less electronic specific heat of numerical value, when there is magnetic phase transition in solid, along with the sharply change of entropy, the specific heat of solid there will be the abnormal phenomenon increased, at below 15K warm area, the magnetic specific heat peak value occurred during magnetic phase transition, often more than an order of magnitude larger than lattice specific heat, for the specific heat realizing low temperature large provides possibility.
Utilize magnetic phase transition than thermal anomaly, find suitable magnetic substance and replace the plumbous work as new low-temperature cold accumulation material, just start as far back as the beginning of the seventies.Much research demonstrates the validity of magnetic cold-storage material, especially Er
3ni, ErNi, Er
3a series of Er such as Co magnetic material is very noticeable as the new opplication of cool storage material in the low temperature technique of below 15K.Er magnetic material Curie temperature, at below 15K, has the Er based material of high full rate and the specific magnetising moment, much bigger at the specific heat of the magnetic phase transition specific heat ratio lead of vicinity of Curie temperatures, they is used for Cryo Refrigerator test, obtains good test-results.After this, utilize magneticsubstance to improve the research of cryogenic refrigeration engine efficiency, constantly making a breakthrough property achievement, become a heat subject in low temperature research field.
But, the application of Er system magnetic cold-storage material still exist the width of specific heat peak narrower, be not easy to problems such as shaping.Because the Er system magnetic cold-storage material magnetic phase transition of crystalline state just occurs in a very narrow temperature range, so the ratio thermal anomaly brought by magnetic phase transition is also just in narrower warm area, the width of specific heat peak is narrower, cause single magnetic cold-storing material can not cover the whole operation temperature area of Cryo Refrigerator, in practical application, need several magnetic cold-storing material to use simultaneously.Research shows, the best of cool storage material uses form to be spherical, be preferably processed into size range in actual applications and use at the spheroidal particle of Φ 154 ~ 300 μm, and it is difficult to be especially processed into spheroidal particle for polycrystalline material.Nodularization about magnetic cold-storage material shapes problem, and scholars has carried out extensive exploration, but effect is unsatisfactory.
Non-crystaline amorphous metal and matrix material thereof are owing to having excellent mechanics and magnetic performance and receiving much concern in recent years.Er base noncrystal alloy has unique non-crystalline state disordered structure, makes it that temperature range broadening of magnetic phase transition occur, and it occurs to be attended by larger magnetic entropy change in the process of magnetic phase transition, may bring large ratio thermal anomaly thus.Therefore, if can at Er
3ni or Er
3the component base of the existing magnetic cold-storage material such as Co is successfully developed Er based bulk amorphous or introduce amorphous phase, develop a kind of cryomagnetism cool storage material having large volume specific heat in wide temperature interval by being expected to.
Summary of the invention
The object of the present invention is to provide a kind of that can be used for Cryo Refrigerator, that there is large Low Temperature Specific Heat erbium base amorphous composite magnetic cold-storage material.
Another object of the present invention is to the preparation method that a kind of above-mentioned erbium base amorphous composite magnetic cold-storage material is provided.
The object of the invention is to realize by the following technical solutions:
The invention provides a kind of erbium base amorphous composite magnetic cold-storage material, this alloy is main component with erbium, at Er
3ni and Er
3formulated on the component base of Co, its composition can be formulated as:
(Er
0.75T
0.25)
aAl
bX
c
Wherein, atomic percent a, b and c meet: 75≤a≤85,15≤b≤25,0≤c≤5, and a+b+c=100;
Element T is Ni or Co;
Element X is selected from one or more in Gd, Tb, Dy, Ho, Tm, Cu, Y, Ag.
The invention provides a kind of preparation method of above-mentioned erbium base amorphous composite magnetic cold-storage material, the method is by selecting suitable element and controlling its atomic percent, and makes it under lower speed of cooling (water-cooled), prepare required amorphous alloy composite material.
Erbium base amorphous composite magnetic cold-storage material of the present invention is having larger volume specific heat lower than in the wider warm area of 15K, and the position of specific heat peak and width-adjustable, Cryo Refrigerator can be applied to as cryomagnetism cool storage material.
Erbium base amorphous composite magnetic cold-storage material provided by the invention is compared with existing low-temperature cold accumulation material, and its advantage is:
1. the required critical cooling rate of erbium base amorphous composite magnetic cold-storage material preparation provided by the invention is low, and preparation method is easy, Heat stability is good, and resistance of oxidation is strong, and the stability used as cryomagnetism cool storage material is stronger.
2. as required, by regulating X element and content thereof, position and the width of the specific heat peak value of required erbium base amorphous composite magnetic cold-storage material can be modulated.
3. compared to traditional cryomagnetism cool storage material, erbium base amorphous composite magnetic cold-storage material provided by the present invention has the superior processing treatment ability in unique supercooling liquid phase region, and thus more easily processing is prepared into tiny particulate state use.
Accompanying drawing explanation
Fig. 1 is erbium base amorphous composite magnetic cold-storage material (Er prepared by the embodiment of the present invention 1
0.75ni
0.25)
80al
17gd
3x-ray diffractogram;
Fig. 2 is erbium base amorphous composite magnetic cold-storage material (Er prepared by the embodiment of the present invention 1
0.75ni
0.25)
80al
17gd
3images of transmissive electron microscope: the selected area electron diffraction image of (a) region I; The selected area electron diffraction image of (b) region II; The selected area electron diffraction image of (c) region III; The high-resolution-ration transmission electric-lens image of (d) region III.
Fig. 3 is erbium base amorphous composite magnetic cold-storage material (Er prepared by the embodiment of the present invention 1
0.75ni
0.25)
80al
17gd
3specific magnetising moment variation with temperature curve;
Fig. 4 is erbium base amorphous composite magnetic cold-storage material (Er prepared by the embodiment of the present invention 1
0.75ni
0.25)
80al
17gd
3with the Low Temperature Specific Heat curve of traditional cool storage material lead;
Fig. 5 is erbium base amorphous composite magnetic cold-storage material (Er prepared by the embodiment of the present invention 2
0.75ni
0.25)
80al
20-xgd
xthe X-ray diffractogram of (x=0,1,2);
Fig. 6 is erbium base amorphous composite magnetic cold-storage material (Er prepared by the embodiment of the present invention 1 and 2
0.75ni
0.25)
80al
17gd
3(Er
0.75ni
0.25)
80al
20the temperature variant curve of the specific magnetising moment;
Fig. 7 is erbium base amorphous composite magnetic cold-storage material (Er prepared by the embodiment of the present invention 1 ~ 4
0.75ni
0.25)
80al
20-xgd
xthe Low Temperature Specific Heat curve of (x=0,1,2,3);
Fig. 8 is erbium base amorphous composite magnetic cold-storage material (Er prepared by the embodiment of the present invention 5 ~ 7
0.75ni
0.25)
80al
17x
3the X-ray diffractogram of (X=Cu, Ho, Y);
Fig. 9 is erbium base amorphous composite magnetic cold-storage material (Er prepared by the embodiment of the present invention 5 ~ 7
0.75ni
0.25)
80al
17x
3the Low Temperature Specific Heat curve of (X=Cu, Ho, Y).
Embodiment
The invention provides a kind of erbium base amorphous composite magnetic cold-storage material, this alloy take erbium as main component, and its composition can be formulated as:
(Er
0.75T
0.25)
aAl
bX
c
Wherein, atomic percent a, b and c meet: 75≤a≤85,15≤b≤25,0≤c≤5, and a+b+c=100;
Element T is Ni or Co;
Element X is selected from one or more in Gd, Tb, Dy, Ho, Tm, Cu, Y, Ag.
In the inventive solutions, by regulating as the X element of trace doped element and content thereof, the per-cent of crystal phase in erbium base amorphous composite magnetic cold-storage material can be modulated on the one hand, and then regulate the width of specific heat peak, the temperature of the magnetic transition of erbium base amorphous composite magnetic cold-storage material can be modulated in addition on the one hand, and then regulate the position of specific heat peak.
The present invention also provides a kind of preparation method of above-mentioned erbium base amorphous composite magnetic cold-storage material, the method is by selecting suitable element and controlling its atomic percent, and makes it under lower speed of cooling (water-cooled), prepare required amorphous alloy composite material.
In technical scheme of the present invention, the preparation method of above-mentioned erbium base amorphous composite magnetic cold-storage material comprises following step:
1) proportioning starting material: by element Er, T, Al and X according to (Er
0.75t
0.25)
aal
bx
cprepare burden, wherein 75≤a≤85,15≤b≤25,0≤c≤5, and a+b+c=100, element T is Ni or Co, and element X is selected from one or more in Gd, Tb, Dy, Ho, Tm, Cu, Y, Ag;
Wherein, the purity of all Er, Co, Ni, Al, Gd, Tb, Dy, Ho, Tm, Cu, Y, Ag elements is all not less than 99.9wt%;
2) preparation of mother alloy: each component of gained of abovementioned steps being prepared burden is placed in the electric arc furnace of the argon atmospher of titanium absorption, and melting (preferably more than 4 times), to make it to mix, obtains mother alloy ingot after cooling;
3) casting is inhaled: use conventional permanent mold casting method, by step 2) obtained mother alloy ingot refuse, utilize the absorbing and casting device in electric arc furnace, the melt of mother alloy is sucked water cooled copper mould, obtains erbium base noncrystal alloy composite magnetic cold-storage material required for the present invention.
Erbium base amorphous composite magnetic cold-storage material of the present invention is having larger volume specific heat lower than in the wider warm area of 15K, and the position of specific heat peak and width-adjustable, Cryo Refrigerator can be applied to as cryomagnetism cool storage material.
Below in conjunction with accompanying drawing, describe embodiments of the present invention in detail with multiple embodiment, these embodiments are only the object of explanation and detailed description, should not be construed as limitation of the present invention.
Embodiment 1, erbium base non-crystalline alloy compound material (Er
0.75ni
0.25)
80al
17gd
3preparation
By material purity be more than 99.9wt% (weight percent) Er, Ni, Al and Gd tetra-kinds of components by molar weight ratio be 60: 20: 17: 3 prepare after, mixing in the electric arc furnace of the argon atmospher of titanium absorption melting 5 times, to make it to mix, obtain the mother alloy ingot of Er-Ni-A1-Gd quad alloy after cooling; Then use conventional metal mould cast method, by this ingot casting refuse, utilize the absorbing and casting device in electric arc furnace, mother alloy melt is sucked water cooled copper mould, can obtain composition is (Er
0.75ni
0.25)
80al
17gd
3, diameter is the erbium base amorphous composite magnetic cold-storage material of 1mm.
Fig. 1 is the erbium base amorphous composite magnetic cold-storage material (Er of this diameter 1 millimeter
0.75ni
0.25)
80al
17gd
3x-ray diffractogram; Shown in Fig. 1, diffuse scattering peak occurs some crystallization peaks, can prove that this alloy is amorphous alloy composite material thus.
And the ratio of crystal shared by amorphous alloy composite material is determined by tem study (TEM).The difference that non-crystalline material shows in electron microscopic analysis method is very little, and the material of crystallization just has very large difference, and is easy to difference.The Crystallization Phases that disperse is separated out in amorphous phase can carry out observation and analysis with transmission electron microscope and high-resolution electron microscope, also can be differentiated by electron diffraction pattern.Erbium base amorphous composite magnetic cold-storage material (Er prepared by the embodiment of the present invention 1
0.75ni
0.25)
80al
17gd
3composite structure can be confirmed further by the transmission electron microscope photo of Fig. 2.Wherein: the electron-diffraction diagram of display area I similarly is the ring of light of a series of disperse in Fig. 2 (a), prove that this region is non-crystalline state completely; Near the disperse ring of light, start the appearance having Bragg diffraction spot in Fig. 2 (b), declare area II has Crystallization Phases to start to separate out; Bragg diffraction spot in Fig. 2 (c) becomes more high-visible, can be found out in the III of region on noncrystal substrate, separated out larger Crystallization Phases by the high resolution transmission image in Fig. 2 (d).
So far, can be determined by above-mentioned X-ray diffraction and images of transmissive electron microscope, erbium base amorphous composite magnetic cold-storage material (Er prepared by the embodiment of the present invention 1
0.75ni
0.25)
80al
17gd
3amorphous alloy composite material really.
Fig. 3 is erbium base amorphous composite magnetic cold-storage material (Er prepared by the embodiment of the present invention 1
0.75ni
0.25)
80al
17gd
3specific magnetising moment variation with temperature curve, as can be seen from the magnetic characteristic curve of this amorphous alloy composite material, (Er
0.75ni
0.25)
80al
17gd
3there is magnetic phase transition lower than in the wide temperature interval of 15k, its null field cold (ZFC) and field cold (FC) curve show the characteristic of spin glass at low temperature bifurcated.
Fig. 4 is erbium base amorphous composite magnetic cold-storage material (Er prepared by the embodiment of the present invention 1
0.75ni
0.25)
80al
17gd
3with the comparison diagram of the Low Temperature Specific Heat curve of traditional cool storage material lead.As can be seen from Figure, plumbous apparently higher than traditional cool storage material at the volume specific heat of this alloy of below 15k, its specific heat anomaly peak occurs at 12K, and the width at peak is 5K, and peak value reaches 0.485J/Kcm
3, than the specific heat of combustion (0.238J/Kcm of the lead at peak temperature place
3) large one times.Therefore, this alloy can be applied to Cryo Refrigerator as cryomagnetism cool storage material.
Embodiment 2 ~ 4, erbium base amorphous composite magnetic cold-storage material (Er
0.75ni
0.25)
80al
20-xgd
xthe preparation of (x=0,1,2)
Be similar to the preparation method of embodiment 1, prepare the erbium base amorphous composite magnetic cold-storage material (Er of diameter 1 millimeter
0.75ni
0.25)
80al
20, (Er
0.75ni
0.25)
80al
19gd
1(Er
0.75ni
0.25)
80al
18gd
2.
Fig. 5 is the X-ray diffractogram of this series of erbium base amorphous composite magnetic cold-storage material, can find out, alloy (Er
0.75ni
0.25)
80al
20, (Er
0.75ni
0.25)
80al
19gd
1(Er
0.75ni
0.25)
80al
18gd
2have and (Er
0.75ni
0.25)
80al
17gd
3the structure of identical amorphous alloy composite material.
Figure 6 shows that (Er prepared by embodiment 2
0.75ni
0.25)
80al
20with (Er prepared by embodiment 1
0.75ni
0.25)
80al
17gd
3the temperature variant curve of the specific magnetising moment, as seen along with the change of gadolinium concentrations makes to there occurs corresponding change between the magnetic transition temperature of material and limited proportionality.
And this change that Fig. 6 reflects correspondingly just result in Low Temperature Specific Heat changes with the change of gadolinium concentrations, as shown in Figure 7.Fig. 7 is the Low Temperature Specific Heat curve of erbium base amorphous composite magnetic cold-storage material prepared by the embodiment of the present invention 1 ~ 4, and as shown in Figure 7, these amorphous alloy composite materials all have higher low temperature volume specific heat of combustion at below 15k.Can be found by the ratio thermal parameter (listing in table 1) obtained than heating curve, the peak value with the specific heat peak of this Amorphous Alloy matrix material of increase of gadolinium concentrations increases gradually and moves to high-temperature area, and the width at its peak increases gradually simultaneously.As can be seen here, can be regulated and controled position and the width of the specific heat peak of this amorphous alloy composite material by the addition controlling gadolinium concentrations, this is just for it provides remarkable advantage as cryomagnetism cool storage material.
Embodiment 5 ~ 7, erbium base amorphous composite magnetic cold-storage material (Er
0.75ni
0.25)
80al
17x
3the preparation of (X=Cu, Ho, Y)
Be similar to the preparation method of embodiment 1, prepare the erbium base amorphous composite magnetic cold-storage material (Er of diameter 1 millimeter
0.75ni
0.25)
80al
17cu
3, (Er
0.75ni
0.25)
80al
17ho
3, (Er
0.75ni
0.25)
80al
17y
3.
Fig. 8 is the X-ray diffractogram of this series of erbium base amorphous composite magnetic cold-storage material, can find out, alloy (Er
0.75ni
0.25)
80al
17cu
3, (Er
0.75ni
0.25)
80al
17ho
3, (Er
0.75ni
0.25)
80al
17y
3have and (Er
0.75ni
0.25)
80al
17gd
3the structure of identical amorphous alloy composite material.
Fig. 9 is the Low Temperature Specific Heat curve of this series of erbium base amorphous composite magnetic cold-storage material, can find out that three kinds of amorphous alloy composite materials that with the addition of different element all have higher low temperature volume specific heat of combustion at below 15k.Can be found by the ratio thermal parameter (listing in table 1) obtained than heating curve, the position of the specific heat peak of this Amorphous Alloy matrix material, peak value and width change with the change of Addition ofelements.As can be seen here, can be regulated and controled position and the width of the specific heat peak of this amorphous alloy composite material by the kind of Addition ofelements, this is similarly it and provides remarkable advantage as cryomagnetism cool storage material.
Embodiment 8 ~ 40, prepare the erbium base amorphous composite magnetic cold-storage material of various proportioning
Prepare the erbium base amorphous compound cryosar magnetic cold-storage material of various proportioning by the method for embodiment 1, its alloying constituent and Low Temperature Specific Heat parameter are listed in table 1.
Table 1, erbium base amorphous compound cryosar magnetic cold-storage material composition and compare thermal parameter
Note: in table, symbol implication is as follows:
The sample diameter size prepared under D---this experiment condition;
T
peak---the position of specific heat anomaly peak;
Δ T
peak---the width of specific heat anomaly peak;
C
pb(T
peak)---the specific heat of combustion of specific heat anomaly peak place lead;
C
peak---the peak value of specific heat anomaly peak.
The result of being tested by the various embodiments described above and performance test, can find out that erbium base amorphous compound cryosar magnetic cold-storage material of the present invention has: preparation method is simple, Heat stability is good, the processing treatment ability that resistance of oxidation is strong and supercooling liquid phase region is superior, and the position of specific heat peak value and width such as can to regulate at the feature, thus have potential application prospect as low temperature magnetic cool storage material.
Claims (6)
1. an erbium base amorphous composite magnetic cold-storage material, the composition of this alloy is formulated as:
(Er
0.75Ni
0.25)
aAl
bX
c
Wherein, atomic percent a, b and c meet: 75≤a≤85,15≤b≤25,0 < c≤5, and a+b+c=100;
Element X is selected from one or more in Gd, Tb, Dy, Ho, Tm, Cu, Y, Ag.
2. erbium base amorphous composite magnetic cold-storage material according to claim 1, it is the alloy that one of following formula represents: (Er
0.75ni
0.25)
80al
19gd
1, (Er
0.75ni
0.25)
80al
18gd
2, (Er
0.75ni
0.25)
80al
17gd
3, (Er
0.75ni
0.25)
80al
17cu
3, (Er
0.75ni
0.25)
80al
17ho
3, (Er
0.75ni
0.25)
80al
17y
3, (Er
0.75ni
0.25)
80al
17cu
1ho
1y
1, (Er
0.75ni
0.25)
85al
14gd
1, (Er
0.75ni
0.25)
83al
16cu
1.
3. prepare the method for erbium base amorphous composite magnetic cold-storage material according to claim 1, the method is by selecting suitable element and controlling its atomic percent, and makes it under lower speed of cooling, prepare required amorphous alloy composite material.
4. preparation method as claimed in claim 3, comprising:
1) proportioning starting material: by element Er, Ni, Al and X according to (Er
0.75ni
0.25)
aal
bx
cprepare burden, wherein 75≤a≤85,15≤b≤25,0 < c≤5, and a+b+c=100, element X are selected from one or more in Gd, Tb, Dy, Ho, Tm, Cu, Y, Ag;
Wherein, the purity of all Er, Ni, Al, Gd, Tb, Dy, Ho, Tm, Cu, Y, Ag elements is all not less than 99.9wt%;
2) preparation of mother alloy: each component of gained of abovementioned steps being prepared burden is placed in the electric arc furnace of the argon atmospher of titanium absorption, and melting, to make it to mix, obtains mother alloy ingot after cooling;
3) casting is inhaled: use permanent mold casting method, by step 2) obtained mother alloy ingot refuse, utilize the absorbing and casting device in electric arc furnace, the melt of mother alloy is sucked water cooled copper mould, obtains required erbium base noncrystal alloy composite magnetic cold-storage material.
5. as claimed in claim 4 preparation method, wherein step 2) in melting number of times more than 4 times.
6. the erbium base amorphous composite magnetic cold-storage material of claim 1 or 2 is as the application of cryomagnetism cool storage material in Cryo Refrigerator.
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| CN106978576B (en) * | 2017-02-28 | 2018-10-23 | 东北大学 | A kind of Er bases amorphous low-temperature magnetic refrigeration material and preparation method thereof |
| 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 |
| CN112981278A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院物理研究所 | High-energy-content amorphous alloy material, and preparation method and application thereof |
| CN110983207B (en) * | 2019-12-17 | 2021-04-27 | 中国科学院宁波材料技术与工程研究所 | Amorphous composite material without Fe, Co and Ni and preparation method and application thereof |
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| CN101550521A (en) * | 2008-04-01 | 2009-10-07 | 中国科学院物理研究所 | Rare-earth-based bulk amorphous alloy with magnetothermal effect and composite material thereof |
| CN101629271A (en) * | 2008-11-11 | 2010-01-20 | 北京科技大学 | Low-temperature magnetic cooling erbium-based bulk amorphous material |
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| CN101629271A (en) * | 2008-11-11 | 2010-01-20 | 北京科技大学 | Low-temperature magnetic cooling erbium-based bulk amorphous material |
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