CN103031501A - Erbium-based amorphous composite magnetic cold storage material, preparation method thereof, and cryogenic refrigerator - Google Patents
Erbium-based amorphous composite magnetic cold storage material, preparation method thereof, and cryogenic refrigerator Download PDFInfo
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- CN103031501A CN103031501A CN2011103001074A CN201110300107A CN103031501A CN 103031501 A CN103031501 A CN 103031501A CN 2011103001074 A CN2011103001074 A CN 2011103001074A CN 201110300107 A CN201110300107 A CN 201110300107A CN 103031501 A CN103031501 A CN 103031501A
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Abstract
The invention relates to an erbium-based amorphous composite magnetic cold storage material. The alloy adopts erbium as main components, is prepared on the basis of components of Er3Ni and Er3Co, and can be formulated as (Er0.75T0.25)aAlbXc. The invention also relates to a preparation method of the erbium-based amorphous composite magnetic cold storage material, and a cryogenic refrigerator containing the erbium-based amorphous composite magnetic cold storage material. The erbium-based amorphous composite magnetic cold storage material has the characteristics that the preparation method is simple, the heat stability is good, the oxidation resistance is strong, excellent processing capacity of a supercooled liquid region, the position and the width of a specific heat peak value can be adjusted, and the like, so that the erbium-based amorphous composite magnetic cold storage material has potential application prospect when being used as a low-temperature magnetic cold storage material.
Description
Technical field
The present invention relates to low-temperature physics and material science, relate to specifically a kind of erbium base amorphous composite magnetic cold-storage material and preparation method, and the Cryo Refrigerator that comprises this erbium base amorphous composite magnetic cold-storage material.
Background technology
Low-temperature refrigeration technology has been widely used in the numerous areas such as meteorology, military affairs, aerospace, cryotronics, hypothermal medicine as the important branch of low temperature technique.High efficiency Cryo Refrigerator has wide application prospect at industrial circle, is subject to extensive concern.Be lower than the low temperature of 15K, the refrigerating efficiency of Cryo Refrigerator depends primarily on the efficient of its regenerator.The regenerator of Cryo Refrigerator is a kind of efficient energy-storing device, and the cool storage material with high heat capacity is stored respectively in the compression and expansion process of refrigeration cycle and released energy, and 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, a little less than the thermal vibration more and more of lattice, the specific heat of solid is also more and more lower.For example, plumbous specific heat is 0.35J/Kcm when 15K
3, 0.009J/Kcm is only arranged when dropping to 4K
3, so low specific heat makes the output cold of cold-storage machine when low temperature be approximately zero, has seriously affected the efficient of refrigerator.Except the less electronic specific heat of lattice specific heat and numerical value, magnetic phase transition when occuring in solid, be accompanied by the rapid variation of entropy, the unusual phenomenon that increases can appear in the specific heat of solid, at the following warm area of 15K, the magnetic specific heat peak value that occurs during magnetic phase transition, provides possibility for realizing the large specific heat of low temperature by often than lattice specific heat large one more than the order of magnitude.
Utilize magnetic phase transition than thermal anomaly, seek suitable magnetic substance and replace plumbous work as new low-temperature cold accumulation material, just begun as far back as the beginning of the seventies.The many validity that studies have shown that magnetic cold-storage material, especially Er
3Ni, ErNi, Er
3A series of Er magnetic materials such as Co are very noticeable as the new application in the low temperature technique of cool storage material below 15K.Er magnetic material Curie temperature has the Er based material of high full rate and the specific magnetising moment below 15K, much bigger at the specific heat of the magnetic phase transition specific heat ratio lead of vicinity of Curie temperatures, and they are used for the Cryo Refrigerator test, has obtained good test-results.After this, utilize magneticsubstance to improve the research of cryogenic refrigeration engine efficiency, continuous making a breakthrough property achievement has become the heat subject in low temperature research field.
Yet the problem such as that Er is that the application of magnetic cold-storage material still exists is narrower than the width of thermal spike, be not easy to shape.Because the Er of crystalline state is that the magnetic cold-storage material magnetic phase transition just occurs in the very narrow temperature range, so the ratio thermal anomaly that is brought by magnetic phase transition also is in narrower warm area, width than thermal spike is narrower, cause single magnetic cold-storing material can not cover the whole operation temperature area of Cryo Refrigerator, need several magnetic cold-storing materials to use simultaneously in the practical application.Studies show that the best of cool storage material uses form to be sphere, preferably be processed in actual applications size range and use at the spheroidal particle of Φ 154～300 μ m, and be processed into especially difficulty of spheroidal particle for polycrystalline material.Nodularization about magnetic cold-storage material shapes problem, and the various countries scholar has carried out extensive exploration, but effect is unsatisfactory.
Non-crystaline amorphous metal and matrix material thereof receive much concern owing to having good mechanics and magnetic performance in recent years.The Er base noncrystal alloy has unique non-crystalline state disordered structure, makes its temperature range broadening that magnetic phase transition occurs, and is attended by larger magnetic entropy change in the process of its generation magnetic phase transition, may bring thus large ratio thermal anomaly.Therefore, if can be at Er
3Ni or Er
3Develop goes out the based bulk amorphous or introducing amorphous phase of Er on the composition basis of the existing magnetic cold-storage material such as Co, will be expected to develop a kind of cryomagnetism cool storage material that large volume specific heat is arranged in the wide temperature interval.
Summary of the invention
The object of the present invention is to provide a kind of erbium base amorphous composite magnetic cold-storage material Cryo Refrigerator, that have large Low Temperature Specific Heat that can be used for.
Another object of the present invention is to provide a kind of preparation method of above-mentioned erbium base amorphous composite magnetic cold-storage material.
The objective 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 take erbium as main component, at Er
3Ni and Er
3Formulated on the composition basis of Co, its composition can be formulated as:
(Er
0.75T
0.25)
aAl
bX
c
Wherein, atomic percent a, b and c satisfy: 75≤a≤85,15≤b≤25,0≤c≤5, and a+b+c=100;
Element T is Ni or Co;
Element X is one or more that are selected among Gd, Tb, Dy, Ho, Tm, Cu, Y, the 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 control its atomic percent, and so that it prepares required amorphous alloy composite material under lower speed of cooling (water-cooled).
Erbium base amorphous composite magnetic cold-storage material of the present invention has larger volume specific heat in being lower than the wider warm area of 15K, and more adjustable than position and the width of thermal spike, can be used as the cryomagnetism cool storage material and is applied to Cryo Refrigerator.
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. to prepare required critical cooling rate low for erbium base amorphous composite magnetic cold-storage material provided by the invention, and the preparation method is easy, Heat stability is good, resistance of oxidation is strong, as the cryomagnetism cool storage material use stable more intense.
2. can as required, by regulating X element and content thereof, modulate position and the width of the ratio thermal peak of required erbium base amorphous composite magnetic cold-storage material.
3. than traditional cryomagnetism cool storage material, erbium base amorphous composite magnetic cold-storage material provided by the present invention has unique superior processing treatment ability of supercooling liquid phase region, thereby easier processing is prepared into tiny particulate state use.
Description of drawings
Fig. 1 is the erbium base amorphous composite magnetic cold-storage material (Er of the embodiment of the invention 1 preparation
0.75Ni
0.25)
80Al
17Gd
3X-ray diffractogram;
Fig. 2 is the erbium base amorphous composite magnetic cold-storage material (Er of the embodiment of the invention 1 preparation
0.75Ni
0.25)
80Al
17Gd
3Images of transmissive electron microscope: (a) the selected area electron diffraction image of regional I; (b) the selected area electron diffraction image of regional II; (c) the selected area electron diffraction image of regional III; (d) high-resolution-ration transmission electric-lens image of regional III.
Fig. 3 is the erbium base amorphous composite magnetic cold-storage material (Er of the embodiment of the invention 1 preparation
0.75Ni
0.25)
80Al
17Gd
3Specific magnetising moment variation with temperature curve;
Fig. 4 is the erbium base amorphous composite magnetic cold-storage material (Er of the embodiment of the invention 1 preparation
0.75Ni
0.25)
80Al
17Gd
3Low Temperature Specific Heat curve with traditional cool storage material lead;
Fig. 5 is the erbium base amorphous composite magnetic cold-storage material (Er of the embodiment of the invention 2 preparations
0.75Ni
0.25)
80Al
20-xGd
xThe X-ray diffractogram of (x=0,1,2);
Fig. 6 is the erbium base amorphous composite magnetic cold-storage material (Er of the embodiment of the invention 1 and 2 preparations
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 the erbium base amorphous composite magnetic cold-storage material (Er of the embodiment of the invention 1～4 preparation
0.75Ni
0.25)
80Al
20-xGd
xThe Low Temperature Specific Heat curve of (x=0,1,2,3);
Fig. 8 is the erbium base amorphous composite magnetic cold-storage material (Er of the embodiment of the invention 5～7 preparations
0.75Ni
0.25)
80Al
17X
3The X-ray diffractogram of (X=Cu, Ho, Y);
Fig. 9 is the erbium base amorphous composite magnetic cold-storage material (Er of the embodiment of the invention 5～7 preparations
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 is 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 satisfy: 75≤a≤85,15≤b≤25,0≤c≤5, and a+b+c=100;
Element T is Ni or Co;
Element X is one or more that are selected among Gd, Tb, Dy, Ho, Tm, Cu, Y, the Ag.
In technical scheme of the present invention, by regulating X element and the content thereof as trace doped element, can modulate the per-cent of crystal phase in the erbium base amorphous composite magnetic cold-storage material on the one hand, and then adjusting is than the width of thermal spike, can modulate on the one hand in addition the temperature of the magnetic transition of erbium base amorphous composite magnetic cold-storage material, and then regulate the position than thermal spike.
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 control its atomic percent, and so that it prepares required amorphous alloy composite material under lower speed of cooling (water-cooled).
In the 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: with 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, element X is one or more that are selected among Gd, Tb, Dy, Ho, Tm, Cu, Y, the Ag;
Wherein, the purity of all Er, Co, Ni, Al, Gd, Tb, Dy, Ho, Tm, Cu, Y, Ag element all is not less than 99.9wt%;
2) preparation of mother alloy: the prepare burden each component of gained of abovementioned steps is placed the electric arc furnace of the argon atmospher of titanium absorption, and melting (preferred more than 4 times) mixes making it, and obtains mother alloy ingot after the cooling;
3) inhale casting: use conventional permanent mold casting method, with step 2) the mother alloy ingot refuse that makes, utilize the absorbing and casting device in the electric arc furnace, the melt suction water cooled copper mould with mother alloy 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 has larger volume specific heat in being lower than the wider warm area of 15K, and more adjustable than position and the width of thermal spike, can be used as the cryomagnetism cool storage material and is applied to Cryo Refrigerator.
Below in conjunction with accompanying drawing, describe embodiments of the present invention in detail with a plurality of embodiment, these embodiment only for the purpose 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
Be that 99.9wt% (weight percent) above Er, Ni, Al and four kinds of components of Gd are 60: 20: 17 by the molar weight ratio with material purity: 3 prepare after, in the electric arc furnace of the argon atmospher of titanium absorption, mix and melting 5 times mixes making it, obtain the mother alloy ingot of Er-Ni-A1-Gd quad alloy after the cooling; Then use conventional metal mould cast method, with this ingot casting refuse, utilize the absorbing and casting device in the electric arc furnace, the 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 1 millimeter of this diameter
0.75Ni
0.25)
80Al
17Gd
3X-ray diffractogram; Can find out from shown in Figure 1, occur some crystallization peaks at the diffuse scattering peak, can prove that thus this alloy is the amorphous alloy matrix material.
Tem study (TEM) is next to be determined and crystal shared ratio in amorphous alloy composite material can be passed through.The difference that non-crystalline material shows in the 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 come observation and analysis with transmission electron microscope and high-resolution electron microscope, also can differentiate by electron diffraction pattern.The erbium base amorphous composite magnetic cold-storage material (Er of the embodiment of the invention 1 preparation
0.75Ni
0.25)
80Al
17Gd
3Composite structure can further confirm 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 disperses among Fig. 2 (a), proves that this zone is non-crystalline state completely; Begin to have the appearance of Bragg diffraction spot among Fig. 2 (b) near the disperse ring of light, declare area II has Crystallization Phases to begin to separate out; Bragg diffraction spot among Fig. 2 (c) becomes more high-visible, can find out among the regional III by the high resolution transmission image among Fig. 2 (d) and separate out larger Crystallization Phases at noncrystal substrate.
So far, can be determined the erbium base amorphous composite magnetic cold-storage material (Er of the embodiment of the invention 1 preparation by above-mentioned X-ray diffraction and images of transmissive electron microscope
0.75Ni
0.25)
80Al
17Gd
3Really amorphous alloy matrix material.
Fig. 3 is the erbium base amorphous composite magnetic cold-storage material (Er of the embodiment of the invention 1 preparation
0.75Ni
0.25)
80Al
17Gd
3Specific magnetising moment variation with temperature curve, can find out (Er by the magnetic characteristic curve of this amorphous alloy composite material
0.75Ni
0.25)
80Al
17Gd
3In being lower than the wide temperature interval of 15k magnetic phase transition occurs, its null field cold (ZFC) and cold (FC) curve have shown the characteristic of spin glass at the low temperature bifurcated.
Fig. 4 is the erbium base amorphous composite magnetic cold-storage material (Er of the embodiment of the invention 1 preparation
0.75Ni
0.25)
80Al
17Gd
3Comparison diagram with the Low Temperature Specific Heat curve of traditional cool storage material lead.As can be seen from Figure, the volume specific heat of this alloy is plumbous apparently higher than traditional cool storage material below 15k, and its specific heat anomaly peak occurs at 12K, and the width at peak is 5K, and peak value has reached 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 used as the cryomagnetism cool storage material and is applied to Cryo Refrigerator.
Be similar to the preparation method of embodiment 1, prepare the erbium base amorphous composite magnetic cold-storage material (Er of 1 millimeter of diameter
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 these a series of erbium base amorphous composite magnetic cold-storage materials, 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 (the Er of embodiment 2 preparations
0.75Ni
0.25)
80Al
20(Er with embodiment 1 preparation
0.75Ni
0.25)
80Al
17Gd
3The temperature variant curve of the specific magnetising moment, as seen along with the variation of gadolinium concentrations so that between the magnetic transition temperature of material and limited proportionality corresponding variation has occured.
And this variation that Fig. 6 reflects has correspondingly just caused Low Temperature Specific Heat to change with the variation of gadolinium concentrations, as shown in Figure 7.Fig. 7 is the Low Temperature Specific Heat curve of the erbium base amorphous composite magnetic cold-storage material of the embodiment of the invention 1～4 preparation, and as shown in Figure 7, these amorphous alloy composite materials all have higher low temperature volume specific heat of combustion below 15k.Can be found that by the ratio thermal parameter (listing in table 1) that obtains than heating curve increase gradually and move to high-temperature area with the peak value of the ratio thermal spike of this Amorphous Alloy matrix material of increase of gadolinium concentrations, the width at its peak increases gradually simultaneously.This shows that can regulate and control position and the width of the ratio thermal spike of this amorphous alloy composite material by the addition of control gadolinium concentrations, this just provides remarkable advantage for it as the cryomagnetism cool storage material.
Be similar to the preparation method of embodiment 1, prepare the erbium base amorphous composite magnetic cold-storage material (Er of 1 millimeter of diameter
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 these a series of erbium base amorphous composite magnetic cold-storage materials, 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 these a series of erbium base amorphous composite magnetic cold-storage materials, can find out that three kinds of amorphous alloy composite materials that added different elements all have higher low temperature volume specific heat of combustion below 15k.Can be found that by the ratio thermal parameter (listing in table 1) that obtains than heating curve position, peak value and the width of the ratio thermal spike of this Amorphous Alloy matrix material changes with the change of adding element.This shows that can regulate and control position and the width of the ratio thermal spike of this amorphous alloy composite material by the kind of adding element, this is similarly it and provides remarkable advantage as the cryomagnetism cool storage material.
The erbium base amorphous composite magnetic cold-storage material of embodiment 8～40, the various proportionings of preparation
Prepare the erbium base amorphous compound cryosar magnetic cold-storage material of various proportionings by the method for embodiment 1, its alloying constituent and Low Temperature Specific Heat parameter are listed in the table 1.
Table 1, erbium base amorphous compound cryosar magnetic cold-storage material composition and compare thermal parameter
Annotate: the symbol implication is as follows in the table:
The sample diameter size for preparing 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.
Result by the various embodiments described above and performance test experiment, can find out that erbium base amorphous compound cryosar magnetic cold-storage material of the present invention has: the preparation method is simple, Heat stability is good, resistance of oxidation reaches by force the superior processing treatment ability of supercooling liquid phase region, and the characteristics such as can regulate than the position of thermal peak and width, thereby as the low temperature magnetic cool storage material potential application prospect is arranged.
Claims (6)
1. erbium base amorphous composite magnetic cold-storage material, the composition of this alloy is formulated as:
(Er
0.75T
0.25)
aAl
bX
c
Wherein, atomic percent a, b and c satisfy: 75≤a≤85,15≤b≤25,0≤c≤5, and a+b+c=100;
Element T is Ni or Co;
Element X is one or more that are selected among Gd, Tb, Dy, Ho, Tm, Cu, Y, the Ag.
2. erbium base amorphous composite magnetic cold-storage material according to claim 1, it is the alloy of one of following formula expression: (Er
0.75Ni
0.25)
75Al
25, (Er
0.75Ni
0.25)
80Al
20, (Er
0.75Ni
0.25)
85Al
15, (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, (Er
0.75Co
0.25)
85Al
15, (Er
0.75Co
0.25)
75Al
22Gd
3
3. the method for preparing erbium base amorphous composite magnetic cold-storage material claimed in claim 1, the method are by selecting suitable element and control its atomic percent, and so that it prepares required amorphous alloy composite material under lower speed of cooling.
4. preparation method as claimed in claim 3 comprises:
1) proportioning starting material: with 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, element X is one or more that are selected among Gd, Tb, Dy, Ho, Tm, Cu, Y, the Ag;
Wherein, the purity of all Er, Co, Ni, Al, Gd, Tb, Dy, Ho, Tm, Cu, Y, Ag element all is not less than 99.9wt%;
2) preparation of mother alloy: the prepare burden each component of gained of abovementioned steps is placed the electric arc furnace of the argon atmospher of titanium absorption, and melting mixes making it, and obtains mother alloy ingot after the cooling;
3) the mother alloy ingot refuse that suction casting: use the permanent mold casting method, with step 2) makes utilizes the absorbing and casting device in the electric arc furnace, and the melt suction water cooled copper mould with mother alloy obtains required erbium base noncrystal alloy composite magnetic cold-storage material.
5. preparation method as claimed in claim 4, wherein step 2) in the melting number of times more than 4 times.
6. claim 1 or 2 erbium base amorphous composite magnetic cold-storage material are as the application of cryomagnetism cool storage material in Cryo Refrigerator.
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| 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 |
| 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 |
| CN110983207A (en) * | 2019-12-17 | 2020-04-10 | 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 |
| 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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