CN106011713B - A kind of preparation method of high refrigerating capacity nickel manganese gallium micron alloying pellet - Google Patents
A kind of preparation method of high refrigerating capacity nickel manganese gallium micron alloying pellet Download PDFInfo
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- CN106011713B CN106011713B CN201610437452.5A CN201610437452A CN106011713B CN 106011713 B CN106011713 B CN 106011713B CN 201610437452 A CN201610437452 A CN 201610437452A CN 106011713 B CN106011713 B CN 106011713B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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Abstract
A kind of preparation method of high refrigerating capacity nickel manganese gallium micron alloying pellet, is related to a kind of preparation method of nickel manganese gallium particle, the present invention in order to solve nickel manganese gallium alloy operating temperature, cryogenic temperature section existing for magnetic process of refrigerastion, the hysteresis of phase transformation is big the problems such as.Method is：First, the preparation of nickel manganese gallium alloy cast ingot；2nd, the cleaning-drying of nickel manganese gallium alloy cast ingot；3rd, the cleaning-drying of quartz ampoule；4th, preparation of samples；Five：Alloy cast ingot homogenization heat treatment；6th, the preparation of micron alloying pellet；7th, micron alloying pellet stress relief annealing is heat-treated；8th, the preparation of hybrid microscale alloying pellet.Mixed Ni manganese gallium alloy particle prepared by the inventive method has good cyclical stability；Phase transition temperature is higher than room temperature, the hysteresis of phase transformation is small, operating temperature section is wide, is a kind of high performance magnetic refrigerating working material so as to have good magnetic refrigerant capacity.The present invention is applied to prepare high refrigerating capacity nickel manganese gallium micron alloying pellet.
Description
Technical field
The present invention relates to a kind of preparation method of high refrigerating capacity nickel manganese gallium micron alloying pellet.
Background technology
In recent years, as the extensive promotion of the idea of sustainable development, environmental problem have obtained increasing concern.Making
In terms of refrigeration technique, conventional refrigeration technology mostly using gas working mediums such as freon and ammonia, environment is caused very big pollution and
Destroy, particularly freon working medium meeting heavy damage atmospheric ozone layer, threaten existence and the safety of the mankind.Asked to solve this
Topic, scientific research personnel are directed to developing floride-free gas working medium, and the great advantage of such working medium is not destroy atmospheric ozone layer, still
The greenhouse effects having mostly, it can not still overcome the inherent shortcoming of compressed gas Refrigeration Technique.
At present, scientific research personnel is still actively seeking some brand-new Refrigeration Techniques.Wherein, magnetic Refrigeration Technique receives scientific research
The extensive concern of personnel, it is acknowledged as a kind of high-tech green refrigeration technology.Magnetic refrigerating material utilizes electronic spin system magnetic
The principle that Entropy Changes changes with external magnetic field, reach refrigeration purpose by changing external magnetic field, be generally accompanied with primary structure phase transformation
Or two level magnetic phase transition produces larger isothermal magnetic entropy and becomes (Δ Sm) or adiabatic temperature change (Δ Tad).Magnetic refrigerating material have this
Kind effect is referred to as magnetothermal effect.Magnetic cooling process utilizes solid working medium and heat transfer water, and entropy density is high, and will not produce hazardous atmosphere
Pollutant or greenhouse gases.Another major advantage of magnetic cooling is its high cooling efficiency, is no more than Kano relative to peak efficiency
The conventional refrigeration technology of Cyclical Theory value 10%, cryomagnetic peak efficiency can reach the 60% of Carnot cycle theoretical value.In addition,
Relative to conventional refrigeration technology, it also has the advantages that low noise, good reliability, small volume, easy care and long lifespan.Therefore,
The research of high-performance magnetism refrigerating material is significant.Wherein, primary structure phase transformation and two level can occur for nickel manganese gallium alloy
Magnetic phase transition, larger magnetothermal effect and very high magnetic response frequency are produced, be expected to turn into new high-performance magnetism refrigerating material.
However, although nickel manganese gallium magnetic refrigerating material has a good application prospect in terms of conventional refrigeration working medium is substituted, but
It is some urgent problems to be solved still be present, mainly including the following aspects：
1st, operating temperature problem, for point of view of practicability, the operating temperature of refrigerating material be preferably located near room temperature or
A little higher than room temperature, 90-100 DEG C or so is stable in greatly yet with the Curie temperature of nickel manganese gallium alloy, therefore how to regulate and control magnetic
Relation between Entropy Changes and operating temperature is most important；
2nd, the regulation and control problem of magnetic entropy change and refrigerating capacity (operation interval), when the first order phase change of nickel manganese gallium alloy and second-order phase transistion
When coupling, magnetic entropy becomes very high；But phase transition temperature interval narrows under couple state, refrigerating capacity is caused to decline；
3rd, lag issues, nickel manganese gallium alloy magnetic refrigeration process can often cause with first order phase change, first order phase change hysteresis
Heat is produced in phase transition process, the generation of this heat can substantially reduce the efficiency of refrigeration；
4th, recycle heat problem, in magnetic cooling cycle system, the heat between medium and refrigerating material is effectively transmitted and followed
Effectively distributing for ring medium heat is most important；
5th, cycle life problem, the magnetic refrigerating material of first order phase change is typically accompanied by due to larger volume occurs in phase transition process
Change, crack initiation even breakage problem easily occurs in multiple magnetic Thermal Cycling and fails, because nickel manganese gallium alloy has
There is intrinsic fragility, may cause bulk alloy that Cracking Failure occurs.Bulk nickel manganese gallium alloy is prepared into micron particles, by micro-
The characteristics of less size of rice grain, larger specific surface area and phase transition temperature easily regulate and control, have at the aspect that solves the above problems
Have great advantage, so as to as a kind of high-performance magnetism refrigerating material.
The content of the invention
The present invention is difficult to adjust, made to solve existing nickel manganese gallium alloy operating temperature present in magnetic process of refrigerastion
Cold temperature range is narrow, the hysteresis of phase transformation is big, it is low with medium heat transference efficiency, be easily broken off in cyclic process the problem of failure, carry
A kind of preparation method of high refrigerating capacity nickel manganese gallium micron alloying pellet is gone out.
The preparation method of the high refrigerating capacity nickel manganese gallium micron alloying pellet of the present invention is carried out according to the following steps：
First, the preparation of nickel manganese gallium alloy cast ingot
According to nickel manganese gallium alloy NixMnyGazMiddle each element ratio preparation raw material, is then prepared using vacuum induction melting furnace
Obtain nickel manganese gallium alloy cast ingot；Wherein x=50%~55%, y=20%~25%, z=(100-x-y) %；
2nd, the cleaning-drying of nickel manganese gallium alloy cast ingot
With 320# sand paper polishing nickel manganese gallium alloy cast ingot surface, the caused oxide skin in preparation process is removed, then will
Nickel manganese gallium alloy cast ingot immerse absolute ethyl alcohol in, be cleaned by ultrasonic 5~10 minutes in supersonic cleaning machine, after the completion of take out nickel manganese gallium
Alloy cast ingot is simultaneously positioned on dry filter paper, and 10min is dried at 60~80 DEG C；It is described be cleaned by ultrasonic processing frequency be
40kHz, power 300W；
3rd, the cleaning-drying of quartz ampoule
Two quartz ampoules that it is 30mm to take external diameter, wall thickness is 1.5mm and external diameter is 9mm, wall thickness is 1.5mm, quartz ampoule
Both ends perforate, and being totally immersed into the container for filling dilute nitric acid solution, then by container be placed in ultrasound 20 in supersonic cleaning machine~
30min, after the completion of take out container and stand 12~24h, cleaned after taking out quartz ampoule from container with distilled water, finally will be after cleaning
Quartz ampoule be put into drying baker, at 100~120 DEG C dry 20~24h；The length of described two quartz ampoules is all 300mm；
The mass fraction of the dilute nitric acid solution is 5%；
4th, preparation of samples
With oxy-acetylene flame, the external diameter that step 3 is handled to obtain is that melting makes its reduced diameter to 3 at 9mm quartz ampoules 1/2
~5mm, and the external diameter that its one end mouth of pipe and step 3 are handled to obtain is docked for one end mouth of pipe of 30mm quartz ampoules and the company of melting
Connect, handling to obtain nickel manganese gallium alloy cast ingot by step 2 is positioned in the quartz ampoule that external diameter is 30mm, by the stone that external diameter is 30mm
The English pipe other end is sealed using oxy-acetylene flame；The interface position that Ti paper tinsels are placed in inside two quartz ampoules；
0.5 × 10 will be evacuated in two quartz ampoules-3~5 × 10-30.1MPa high-purity argon gas is filled with after Pa, then
It is repeated twice and vacuumizes and be filled with high-purity argon gas operation, finally will be evacuated to 5 × 10 in quartz ampoule-3Oxy-acetylene flame is utilized after Pa
External diameter is melting sealed for the quartz ampoule at 3~5mm；The thickness of the Ti paper tinsels is 100 μm；Ti paper tinsels have the energy of strong absorption oxygen
Power, it can prevent nickel manganese gallium alloy cast ingot from aoxidizing in subsequent heat insulating process；
5th, alloy cast ingot homogenization heat treatment
The sealed silica envelope that step 4 is obtained is placed in resistance furnace, and 900 are warming up to 5~10 DEG C/min firing rate
~950 DEG C and 24~48h of insulation, insulation terminates rear furnace cooling to room temperature, obtains the alloy cast ingot of homogenization heat treatment；
6th, the preparation of micron alloying pellet
The alloy cast ingot that the homogenization that step 5 is obtained is heat-treated is using Wire EDM into height for 8~10mm's
Cylindric alloy cast ingot, cut surface is polished to remove cutting vestige with 320# sand paper, then soaks the cylindric alloy after polishing
Enter ultrasonic wave cleaning in acetone soln and remove surface and oil contaminant, then cylindric alloy is put into drying box, it is dry at 60~80 DEG C
Dry 10min；
Dried cylindric alloy cast ingot is crushed, the cylindric alloy cast ingot of crushing ground with agate mortar
Mill, then sieved with standard sample and the alloying pellet obtained after grinding is screened to obtain the alloy that particle diameter is 38.5~710 μm
Grain, by alloying pellet and immerses in acetone soln, is cleaned by ultrasonic 5~10 minutes, and last drying process obtains a micron alloy
Grain；
The step of drying process is：In drying box 10min is dried at 60~80 DEG C；
7th, micron alloying pellet stress relief annealing is heat-treated
It is 9mm to take external diameter, wall thickness 1.5mm, long 300mm through hole quartz ampoule, and is cleaned with the method for step 3
Dry, first with oxy-acetylene flame by the end closure of quartz ampoule one, then its external diameter will be made with oxy-acetylene flame melting at quartz ampoule 1/3 and 2/3
3mm is contracted to, the micron alloying pellet that step 6 obtains is positioned over quartzy seal of tube one end, takes 100 μ m-thick Ti paper tinsels to be placed in stone
At 1/2 inside English pipe, wherein ensureing not contacting to prevent both from reacting at high temperature between micron alloying pellet and Ti paper tinsels；
Then quartz ampoule is evacuated to 0.5~5 × 10-30.1MPa high-purity argon gas is filled with after Pa, then again vacuumizes quartz ampoule
To 0.5~5 × 10-30.1MPa high-purity argon gas is filled with after Pa, quartz ampoule is finally evacuated to 0.5~5 × 10 again-3Pa, take out
The external diameter that will be close to open at one end while vacuum using oxy-acetylene flame is melting sealed at the quartz ampoule at 3mm；
Quartz ampoule after sealing is put into high temperature resistance furnace, 450~550 are warming up to 5~10 DEG C/min of firing rates
20~24h is incubated after DEG C, last quartz ampoule furnace cooling to room temperature, that is, is completed at the stress relief annealing heat of micron alloying pellet
Reason；
8th, the preparation of hybrid microscale alloying pellet
The method of repeat step one to seven, repeat to change Ni every timexMnyGazThe value of middle x, y, z, ensure to repeat every time
The element ratio of obtained micron alloying pellet is different, and the different micron alloying pellet of two or more element ratios is mixed
Afterwards, immersing in the container equipped with absolute ethyl alcohol, carry out mechanical agitation, mechanical agitation is ultrasonically treated simultaneously, after the completion of, remove
Absolute ethyl alcohol in container, container is placed in dry case, dries 10min at 60~80 DEG C, that is, complete；
The step of supersound process is：It is ultrasonically treated in the supersonic generator that power is 300W, frequency is 40kHz
30~40min；The step of mechanical agitation is：Using the mechanical agitation oar matched with inside diameter of vessel, with 300 revs/min of rotating speed
Stir 40min；
The present invention possesses following beneficial effect：
First, the inventive method can prepare 600~710 μm, 63~96 μm, 50~63 μm, 45~50 μm and 38.5~45 μ
The different-grain diameters such as m, the nickel manganese gallium alloying pellet with different phase transition temperatures, the planted agent in particle can be removed by heat treatment
Power；The micron alloying pellet of acquisition, phase transition temperature be located near room temperature or higher than room temperature, the hysteresis of phase transformation is small, operating temperature section
It is wide, to have big specific surface area, each particle be a small monocrystalline, be not susceptible to be broken in multiple magnetic Thermal Cycling, follow
Ring stability is good；
2nd, by the way that the alloying pellet of different phase transition temperatures is carried out into mixed uniformly method, acquisition mixes the inventive method
Alloying pellet is closed, phase transition temperature is higher than room temperature, the hysteresis of phase transformation is small, operating temperature section is wide, so as to good magnetic refrigeration energy
Power, it is a kind of high performance magnetic refrigerating working material；
3rd, the huge specific surface area that mixed Ni manganese gallium alloy particle prepared by the inventive method has, in practical application mistake
It is big with heat transfer medium heat exchange area in journey, enhance the heat transfer effect with circulatory mediator；
4th, mixed Ni manganese gallium alloy particle prepared by the inventive method is not susceptible to crack initiation in multiple cyclic process
And fracture, so as to have good cyclical stability；
Brief description of the drawings
Fig. 1 is Ni prepared by one step 5 of experiment54.0Mn21.16Ga24.84The photomacrograph of alloy cast ingot；
Fig. 2 is Ni prepared by one step 5 of experiment54.0Mn21.16Ga24.84The edge room temperature metallographic structure photo of alloy cast ingot；
Fig. 3 is Ni prepared by one step 5 of experiment54.0Mn21.16Ga24.84The center portion room temperature metallographic structure photo of alloy cast ingot；
Fig. 4~Fig. 8 be respectively test a step 6 prepare particle diameter for 600~710 μm, 63~96 μm, 50~63 μm, 45
~50 μm and 38.5~45 μm of Ni54.0Mn21.16Ga24.84Micron alloying pellet pattern photo；
Fig. 9 is the Ni that the particle diameter that one step 7 of experiment obtains is 38.5~45 μm54.0Mn21.16Ga24.84Micron alloying pellet
Room temperature metallographic structure photo；
Figure 10 is to test the Ni that the particle diameter that a step 8 obtains all is 38.5~45 μm54.0Mn21.16Ga24.84Micron alloy
Grain and Ni54.78Mn20.73Ga24.49Micron alloying pellet presses quality 1:The pattern photo of 1 mixing；
Figure 11 is the Ni that the particle diameter that one step 7 of experiment obtains is 38.5~45 μm54.0Mn21.16Ga24.84Micron alloying pellet
The intensity of magnetization-temperature curve；
Figure 12 is to test the Ni that particle diameter after the obtained stress relief annealing of a step 7 is 38.5~45 μm54.0Mn21.16Ga24.84
The magnetization curve figure of micron alloying pellet；
Figure 13 is the Ni that the particle diameter that one step 8 of experiment obtains is 38.5~45 μm54.0Mn21.16Ga24.84Micron alloy
Grain and Ni54.78Mn20.73Ga24.49Micron alloying pellet presses quality 1:The magnetic entropy of 1 mixing becomes Δ SmWith the graph of a relation of temperature；
Figure 14 is one step 4 preparation of samples schematic diagram of experiment, and 1 is alloy cast ingot, and 2 be Ti paper tinsels, and 3 be external diameter 9mm quartz
At pipe 1/2,4 be external diameter 30mm quartz ampoule, and 5 be external diameter 9mm quartz ampoule；
Figure 15 prepares schematic diagram for one step 7 micron alloying pellet stress relief annealing heat treated sample of experiment, and 1 is micron
Alloying pellet, 2 be Ti paper tinsels, and 3 be at external diameter 9mm quartz ampoule 1/3, and 4 be at external diameter 9mm quartz ampoule 2/3.
Embodiment：
Technical solution of the present invention is not limited to act embodiment set forth below, in addition between each embodiment
Any reasonable combination.
Embodiment one：A kind of preparation method of high refrigerating capacity nickel manganese gallium micron alloying pellet of present embodiment is pressed
Following steps are carried out：
First, the preparation of nickel manganese gallium alloy cast ingot
According to nickel manganese gallium alloy NixMnyGazMiddle each element ratio preparation raw material, is then prepared using vacuum induction melting furnace
Obtain nickel manganese gallium alloy cast ingot；Wherein x=50%~55%, y=20%~25%, z=(100-x-y) %；
2nd, the cleaning-drying of nickel manganese gallium alloy cast ingot
With 320# sand paper polishing nickel manganese gallium alloy cast ingot surface, the caused oxide skin in preparation process is removed, then will
Nickel manganese gallium alloy cast ingot immerse absolute ethyl alcohol in, be cleaned by ultrasonic 5~10 minutes in supersonic cleaning machine, after the completion of take out nickel manganese gallium
Alloy cast ingot is simultaneously positioned on dry filter paper, and 10min is dried at 60~80 DEG C；
3rd, the cleaning-drying of quartz ampoule
Two quartz ampoules that it is 30mm to take external diameter, wall thickness is 1.5mm and external diameter is 9mm, wall thickness is 1.5mm, quartz ampoule
Both ends perforate, and being totally immersed into the container for filling dilute nitric acid solution, then by container be placed in ultrasound 20 in supersonic cleaning machine~
30min, after the completion of take out container and stand 12~24h, cleaned after taking out quartz ampoule from container with distilled water, finally will be after cleaning
Quartz ampoule be put into drying baker, at 100~120 DEG C dry 20~24h；The length of described two quartz ampoules is all 300mm；
The mass fraction of the dilute nitric acid solution is 5%；
4th, preparation of samples
With oxy-acetylene flame, the external diameter that step 3 is handled to obtain is that melting makes its reduced diameter to 3 at 9mm quartz ampoules 1/2
~5mm, and the external diameter that its one end mouth of pipe and step 3 are handled to obtain is docked for one end mouth of pipe of 30mm quartz ampoules and the company of melting
Connect, handling to obtain nickel manganese gallium alloy cast ingot by step 2 is positioned in the quartz ampoule that external diameter is 30mm, by the stone that external diameter is 30mm
The English pipe other end is sealed using oxy-acetylene flame；The interface position that Ti paper tinsels are placed in inside two quartz ampoules；
0.5 × 10 will be evacuated in two quartz ampoules-3~5 × 10-30.1MPa high-purity argon gas is filled with after Pa, then
It is repeated twice and vacuumizes and be filled with high-purity argon gas operation, finally will be evacuated to 5 × 10 in quartz ampoule-3Oxy-acetylene flame is utilized after Pa
External diameter is melting sealed for the quartz ampoule at 3~5mm；
5th, alloy cast ingot homogenization heat treatment
The sealed silica envelope that step 4 is obtained is placed in resistance furnace, and 900 are warming up to 5~10 DEG C/min firing rate
~950 DEG C and 24~48h of insulation, insulation terminates rear furnace cooling to room temperature, obtains the alloy cast ingot of homogenization heat treatment；
6th, the preparation of micron alloying pellet
The alloy cast ingot that the homogenization that step 5 is obtained is heat-treated is using Wire EDM into height for 8~10mm's
Cylindric alloy cast ingot, cut surface is polished to remove cutting vestige with 320# sand paper, then soaks the cylindric alloy after polishing
Enter ultrasonic wave cleaning in acetone soln and remove surface and oil contaminant, then cylindric alloy is put into drying box, it is dry at 60~80 DEG C
Dry 10min；
Dried cylindric alloy cast ingot is crushed, the cylindric alloy cast ingot of crushing ground with agate mortar
Mill, then sieved with standard sample and the alloying pellet obtained after grinding is screened to obtain the alloy that particle diameter is 38.5~710 μm
Grain, by alloying pellet and immerses in acetone soln, is cleaned by ultrasonic 5~10 minutes, and last drying process obtains a micron alloy
Grain；
7th, micron alloying pellet stress relief annealing is heat-treated
It is 9mm to take external diameter, wall thickness 1.5mm, long 300mm through hole quartz ampoule, and is cleaned with the method for step 3
Dry, first with oxy-acetylene flame by the end closure of quartz ampoule one, then its external diameter will be made with oxy-acetylene flame melting at quartz ampoule 1/3 and 2/3
3mm is contracted to, the micron alloying pellet that step 6 obtains is positioned over quartzy seal of tube one end, takes 100 μ m-thick Ti paper tinsels to be placed in stone
At 1/2 inside English pipe, wherein ensureing not contacting to prevent both from reacting at high temperature between micron alloying pellet and Ti paper tinsels；
Then quartz ampoule is evacuated to 0.5~5 × 10-30.1MPa high-purity argon gas is filled with after Pa, then again vacuumizes quartz ampoule
To 0.5~5 × 10-30.1MPa high-purity argon gas is filled with after Pa, quartz ampoule is finally evacuated to 0.5~5 × 10 again-3Pa, take out
The external diameter that will be close to open at one end while vacuum using oxy-acetylene flame is melting sealed at the quartz ampoule at 3mm；
Quartz ampoule after sealing is put into high temperature resistance furnace, 450~550 are warming up to 5~10 DEG C/min of firing rates
20~24h is incubated after DEG C, last quartz ampoule furnace cooling to room temperature, that is, is completed at the stress relief annealing heat of micron alloying pellet
Reason；
8th, the preparation of hybrid microscale alloying pellet
The method of repeat step one to seven, repeat to change Ni every timexMnyGazThe value of middle x, y, z, ensure to repeat every time
The element ratio of obtained micron alloying pellet is different, and the different micron alloying pellet of two or more element ratios is mixed
Afterwards, immersing in the container equipped with absolute ethyl alcohol, carry out mechanical agitation, mechanical agitation is ultrasonically treated simultaneously, after the completion of, remove
Absolute ethyl alcohol in container, container is placed in dry case, dries 10min at 60~80 DEG C, that is, complete.
Present embodiment possesses following beneficial effect：
First, present embodiment method can prepare 600~710 μm, 63~96 μm, 50~63 μm, 45~50 μm and 38.5
~45 μm of nickel manganese gallium alloying pellets for waiting different-grain diameter, having different phase transition temperatures, can be removed in particle by heat treatment
Internal stress；The micron alloying pellet of acquisition, phase transition temperature be located near room temperature or higher than room temperature, the hysteresis of phase transformation is small, operating temperature
It is a small monocrystalline that section is wide, has big specific surface area, each particle, is not susceptible to break in multiple magnetic Thermal Cycling
Split, good cycling stability；
2nd, present embodiment method is obtained by the way that the alloying pellet of different phase transition temperatures is carried out into mixed uniformly method
Hybrid alloys particle, phase transition temperature is higher than room temperature, the hysteresis of phase transformation is small, operating temperature section is wide, so as to having good magnetic system
Cold energy power, it is a kind of high performance magnetic refrigerating working material；
3rd, the huge specific surface area that mixed Ni manganese gallium alloy particle prepared by present embodiment method has, actually should
It is big with heat transfer medium heat exchange area during, enhance the heat transfer effect with circulatory mediator；
4th, mixed Ni manganese gallium alloy particle prepared by present embodiment method is not susceptible to crackle in multiple cyclic process
Germinating and fracture, so as to have good cyclical stability；
Embodiment two：Present embodiment is unlike embodiment one：Ultrasonic cleaning described in step 2
The frequency of processing is 40kHz, power 300W.It is other identical with embodiment one.
Embodiment three：Present embodiment is unlike embodiment one or two：Ti paper tinsels described in step 4
Thickness be 100 μm.It is other identical with embodiment one or two.
Embodiment four：Unlike one of present embodiment and embodiment one to three：Described in step 6
The step of drying process is：In drying box 10min is dried at 60~80 DEG C.One of other and embodiment one to three
It is identical.
Embodiment five：Unlike one of present embodiment and embodiment one to three：Described in step 6
Dried cylindric alloy cast ingot is crushed, the cylindric alloy cast ingot of crushing is ground with agate mortar, Ran Houyong
Standard sample sieve is screened to obtain the alloying pellet that particle diameter is 38.5~45 μm to the alloying pellet obtained after grinding.Other and tool
One of body embodiment one to four is identical.
Embodiment six：Unlike one of present embodiment and embodiment one to five：Described in step 8
The step of mechanical agitation is：Using the mechanical agitation oar matched with inside diameter of vessel, with 300 revs/min of stirring 40min of rotating speed.It is other
It is identical with one of embodiment one to five.
Embodiment seven：Unlike one of present embodiment and embodiment one to six：Described in step 8
The step of supersound process is：30~40min is ultrasonically treated in the supersonic generator that power is 300W, frequency is 40kHz.Its
It is identical with one of embodiment one to six.
With following verification experimental verification beneficial effects of the present invention：
Experiment one：
The preparation method of the high refrigerating capacity nickel manganese gallium micron alloying pellet of this experiment is carried out according to the following steps：
First, the preparation of nickel manganese gallium alloy cast ingot
According to nickel manganese gallium alloy NixMnyGazMiddle each element ratio preparation raw material, is then prepared using vacuum induction melting furnace
Obtain nickel manganese gallium alloy cast ingot；Wherein x=54.0, y=21.16, z=24.84；
2nd, the cleaning-drying of nickel manganese gallium alloy cast ingot
With 320# sand paper polishing nickel manganese gallium alloy cast ingot surface, the caused oxide skin in preparation process is removed, then will
Nickel manganese gallium alloy cast ingot immerse absolute ethyl alcohol in, is cleaned by ultrasonic 8 minutes in supersonic cleaning machine, after the completion of taking-up nickel manganese gallium alloy
Ingot casting is simultaneously positioned on dry filter paper, and 10min is dried at 70 DEG C；The frequency for being cleaned by ultrasonic processing is 40kHz, and power is
300W；
3rd, the cleaning-drying of quartz ampoule
Two quartz ampoules that it is 30mm to take external diameter, wall thickness is 1.5mm and external diameter is 9mm, wall thickness is 1.5mm, quartz ampoule
Both ends perforate, and be totally immersed into the container for filling dilute nitric acid solution, then container is placed in supersonic cleaning machine ultrasonic
15min, after the completion of take out container and stand 18h, cleaned after taking out quartz ampoule from container with distilled water, finally by the stone after cleaning
English pipe is put into drying baker, and 22h is dried at 100 DEG C；The length of described two quartz ampoules is all 300mm；The dust technology is molten
The mass fraction of liquid is 5%；
4th, preparation of samples
With oxy-acetylene flame, the external diameter that step 3 is handled to obtain is that melting makes its reduced diameter extremely at 9mm quartz ampoules 1/2
3mm, and its one end mouth of pipe is docked and melted for one end mouth of pipe of 30mm quartz ampoules with the external diameter that step 3 handles to obtain and is connected,
Handle to obtain nickel manganese gallium alloy cast ingot by step 2 to be positioned in the quartz ampoule that external diameter is 30mm, by the quartz ampoule that external diameter is 30mm
The other end is sealed using oxy-acetylene flame；The interface position that Ti paper tinsels are placed in inside two quartz ampoules；
5 × 10 will be evacuated in two quartz ampoules-30.1MPa high-purity argon gas is filled with after Pa, is then repeated twice and takes out very
Sky operates with high-purity argon gas is filled with, and finally will be evacuated to 5 × 10 in quartz ampoule-3Using oxy-acetylene flame by external diameter it is 3mm after Pa
The quartz ampoule at place is melting sealed；The thickness of the Ti paper tinsels is 100 μm；
Five：Alloy cast ingot homogenization heat treatment
The sealed silica envelope that step 4 is obtained is placed in resistance furnace, and 900 DEG C are warming up to 10 DEG C/min firing rate
And 24h is incubated, insulation terminates rear furnace cooling to room temperature, obtains the alloy cast ingot of homogenization heat treatment；
6th, the preparation of micron alloying pellet
Circle of the alloy cast ingot that the homogenization that step 5 is obtained is heat-treated using Wire EDM into height for 10mm
Post alloy ingot casting, cut surface is polished to remove cutting vestige with 320# sand paper, then immerses the cylindric alloy after polishing
Ultrasonic wave cleaning removes surface and oil contaminant in acetone soln, then cylindric alloy is put into drying box, in 80 DEG C of dryings
10min；
Dried cylindric alloy cast ingot is crushed, the cylindric alloy cast ingot of crushing ground with agate mortar
Mill, then sieved with standard sample the alloying pellet that is obtained after grinding is screened to obtain particle diameter for 600~710 μm, 63~96 μm,
50~63 μm, 45~50 μm and 38.5~45 μm of alloying pellet；
Wherein, by particle diameter be 38.5~45 μm alloying pellet and immerse in acetone soln, be cleaned by ultrasonic 10 minutes, finally
Drying process obtains a micron alloying pellet；The step of drying process is：In drying box 10min is dried at 80 DEG C；
7th, micron alloying pellet stress relief annealing is heat-treated
It is 9mm to take external diameter, wall thickness 1.5mm, long 300mm through hole quartz ampoule, and is cleaned with the method for step 3
Dry, first with oxy-acetylene flame by the end closure of quartz ampoule one, then its external diameter will be made with oxy-acetylene flame melting at quartz ampoule 1/3 and 2/3
3mm is contracted to, the micron alloying pellet that step 6 obtains is positioned over quartzy seal of tube one end, takes 100 μ m-thick Ti paper tinsels to be placed in stone
At 1/2 inside English pipe, wherein ensureing not contacting to prevent both from reacting at high temperature between micron alloying pellet and Ti paper tinsels；
Then quartz ampoule is evacuated to 5 × 10-30.1MPa high-purity argon gas is filled with after Pa, quartz ampoule is then evacuated to 5 again ×
10-30.1MPa high-purity argon gas is filled with after Pa, quartz ampoule is finally evacuated to 5 × 10 again-3Pa, utilized while vacuumizing
The external diameter that oxy-acetylene flame will be close to open at one end is melting sealed at the quartz ampoule at 3mm；
Quartz ampoule after sealing is put into high temperature resistance furnace, 450~550 are warming up to 5~10 DEG C/min of firing rates
24h is incubated after DEG C, last quartz ampoule furnace cooling to room temperature, that is, completes the stress relief annealing heat treatment of micron alloying pellet；
8th, the preparation of hybrid microscale alloying pellet
The method of repeat step one to seven, change NixMnyGazThe value of middle x, y, z is x=54.78, y=20.73, z=
24.49, it is 38.5~45 μm of Ni to obtain particle diameter54.0Mn21.16Ga24.84Micron alloying pellet and to particle diameter be 38.5~45 μ
mNi54.78Mn20.73Ga24.49Micron alloying pellet, by Ni54.0Mn21.16Ga24.84Micron alloying pellet and Ni54.78Mn20.73Ga24.49
Micron alloying pellet in mass ratio 1:1 is immersed in the container equipped with absolute ethyl alcohol, carries out mechanical agitation, and mechanical agitation is carried out simultaneously
It is ultrasonically treated, after the completion of, remove absolute ethyl alcohol in container, container is placed in dry case, 10min is dried at 60~80 DEG C, i.e., it is complete
Into.
The mass concentration of the alcoholic solution is 30%；The step of mechanical agitation is：Matched using with inside diameter of vessel
Mechanical agitation oar, with 300 revs/min of rotating speed stirring 40min；The step of supersound process is：Power be 300W, frequency be
40min is ultrasonically treated in 40kHz supersonic generator.
Carry out following test and verify this experiment：
Fig. 1 is Ni prepared by step 554.0Mn21.16Ga24.84The photomacrograph of alloy cast ingot, Fig. 2 are rapid five preparations
Ni54.0Mn21.16Ga24.84The edge room temperature metallographic structure photo of alloy cast ingot, Fig. 3 are prepared by step 5
Ni54.0Mn21.16Ga24.84The center portion room temperature metallographic structure photo of alloy cast ingot；From Fig. 2 and Fig. 3, alloy edge after heat treatment
For column crystal, center portion is equiax crystal, crystallite dimension is counted knowable to, the mean breadth of column crystal is about 97 μm, equiax crystal
Crystallite dimension is about 122 μm；
Take the unannealed heat treatment obtained in step 6 particle diameter distinguish 600~710 μm, 63~96 μm, 50~63 μm, 45
~50 μm and 38.5~45 μm of micron alloying pellet simultaneously obtains its pattern photo, respectively such as Fig. 4, Fig. 5, Fig. 6, Fig. 7 and Fig. 8 institutes
Show, understand that when the particle size of micron alloying pellet is larger, major diameter is bigger, and particle diameter is by Fig. 4, Fig. 5, Fig. 6, Fig. 7 and Fig. 8
The average value of 600~710 μm of particle aspect ratios is about 3；As particle size reduces, draw ratio is gradually reduced, and particle tends to ball
Shape；
The room temperature metallographic structure of 38.5~45 μm of micron alloying pellet of the annealing heat-treats that testing procedure seven obtains is shone
Piece, test result is as shown in figure 9, it can be seen that martensite orientation is consistent inside each particle, due to nickel manganese gallium material
Intrinsic fragility, in process of lapping, alloy tends to from grain boundary separation, it was found from crystallite dimension is counted from Fig. 2 and Fig. 3,
The mean breadth of column crystal is about 97 μm, and equiax crystal crystallite dimension is about 122 μm, is all higher than 38.5~45 μm of grain diameter；Separately
It is outer according to only existing a kind of martensite variants in Fig. 9, it is possible thereby to determine, particle diameter is 38.5~45 μm of nickel manganese gallium micron alloy
Particle is monocrystalline state；
Figure 10 is that the particle diameter that step 8 obtains all is 38.5~45 μm of Ni54.0Mn21.16Ga24.84Micron alloying pellet and
Ni54.78Mn20.73Ga24.49Micron alloying pellet presses quality 1:The pattern photo of 1 mixing；
Figure 11 is the Ni that the particle diameter that step 7 obtains is 38.5~45 μm54.0Mn21.16Ga24.84Micron alloying pellet magnetization is strong
Degree-temperature curve, curve 1 is the intensity of magnetization~temperature curve under magnetic field intensity is 50000Oe in figure, and curve 2 is that magnetic field is strong
Spend for the intensity of magnetization~temperature curve under 100Oe, the first derivative maximum for taking lifting/lowering temperature conditional curve herein is phase transformation peak
It is 316.2~322.8K to be worth temperature Ap and Mp, Ap, and Mp is 321.1~326.1K, is evaluated with the difference of Ap and Mp under same magnetic field
Thermo-lag size in phase transition process, it can be seen that thermo-lag value is about 3.3K under 50000Oe, much smaller than bulk
Polycrystalline material (about 10K)；
Figure 12 is the Ni that particle diameter is 38.5~45 μm after the stress relief annealing that step 7 obtains54.0Mn21.16Ga24.84Micron closes
The magnetization curve figure of gold grain, the temperature in figure corresponding to curve be from top to bottom followed successively by 309K, 311K, 313K, 315K,
317K, 323K, 329K, 331K, 333K, 336K and 339K；As shown in Figure 12, particle adds magnetic to be essentially coincided with demagnetizing curve,
Magnetic lag average value is only about 1.97J/kg under 50000Oe, identical with thermo-lag, and the reduction of magnetic lag is also to rely on micron
Magnetic domain wall movement resistance under magnetic fields caused by the reduction of defect and internal stress after the high-specific surface area of grain and heat treatment
Reduce；
Figure 13 is the Ni that the particle diameter that one step 8 of experiment obtains is 38.5~45 μm54.0Mn21.16Ga24.84Micron alloy
Grain and Ni54.78Mn20.73Ga24.49Micron alloying pellet presses quality 1:The magnetic entropy of 1 mixing becomes Δ SmWith the graph of a relation of temperature, in figure
The magnetic field intensity of curve is from top to bottom followed successively by 50kOe, 49kOe, and 48kOe ... ... 1kOe, a are cryogenic temperature section；From Figure 13
In as can be seen that have two magnetic thermal spikes in curve, correspond respectively to the different phase transition temperatures of two kinds of particles, and due to both phases
Temperature difference moderate (~30K) and reached the effect of two magnetic thermal spike consecutive variations；The mixing of nickel manganese gallium micron alloying pellet is big
It is big to add cryogenic temperature section (halfwidth FWHM is~42K) so that the refrigeration of nickel manganese gallium alloy under 50000Oe magnetic field intensities
Ability value (RC) is greatly improved, and has been reached~175J/Kg, has been significantly improved than single particle or bulk alloy；
Figure 14 is step 4 preparation of samples schematic diagram, and 1 is alloy cast ingot, and 2 be Ti paper tinsels, and 3 be external diameter 9mm quartz ampoule 1/2
Place, 4 be external diameter 30mm quartz ampoule, and 5 be external diameter 9mm quartz ampoule；
Figure 15 is that step 7 micron alloying pellet stress relief annealing heat treated sample prepares schematic diagram, and 1 is micron alloy
Grain, 2 be Ti paper tinsels, and 3 be at external diameter 9mm quartz ampoule 1/3, and 4 be at external diameter 9mm quartz ampoule 2/3.
Claims (7)
1. a kind of preparation method of high refrigerating capacity nickel manganese gallium micron alloying pellet, it is characterised in that the preparation method presses following step
It is rapid to carry out：
First, the preparation of nickel manganese gallium alloy cast ingot
According to nickel manganese gallium alloy NixMnyGazMiddle each element ratio preparation raw material, is then prepared using vacuum induction melting furnace
Nickel manganese gallium alloy cast ingot；Wherein x=50%~55%, y=20%~25%, z=(100-x-y) %；
2nd, the cleaning-drying of nickel manganese gallium alloy cast ingot
With 320# sand paper polishing nickel manganese gallium alloy cast ingot surface, the caused oxide skin in preparation process is removed, then by nickel manganese
Gallium alloy ingot casting immerse absolute ethyl alcohol in, is cleaned by ultrasonic 5~10 minutes in supersonic cleaning machine, after the completion of taking-up nickel manganese gallium alloy
Ingot casting is simultaneously positioned on dry filter paper, and 10min is dried at 60~80 DEG C；
3rd, the cleaning-drying of quartz ampoule
Two quartz ampoules that it is 30mm to take external diameter, wall thickness is 1.5mm and external diameter is 9mm, wall thickness is 1.5mm, the both ends of quartz ampoule
Perforate, and being totally immersed into the container for filling dilute nitric acid solution, then by container be placed in ultrasound 20 in supersonic cleaning machine~
30min, after the completion of take out container and stand 12~24h, cleaned after taking out quartz ampoule from container with distilled water, finally will be after cleaning
Quartz ampoule be put into drying baker, at 100~120 DEG C dry 20~24h；The length of described two quartz ampoules is all 300mm；
The mass fraction of the dilute nitric acid solution is 5%；
4th, preparation of samples
With oxy-acetylene flame, the external diameter that step 3 is handled to obtain be at 9mm quartz ampoules 1/2 melting make its reduced diameter to 3~
5mm, and its one end mouth of pipe is docked and melted for one end mouth of pipe of 30mm quartz ampoules with the external diameter that step 3 handles to obtain and is connected,
Handle to obtain nickel manganese gallium alloy cast ingot by step 2 to be positioned in the quartz ampoule that external diameter is 30mm, by the quartz ampoule that external diameter is 30mm
The other end is sealed using oxy-acetylene flame；The interface position that Ti paper tinsels are placed in inside two quartz ampoules；
0.5 × 10 will be evacuated in two quartz ampoules-3~5 × 10-30.1MPa high-purity argon gas is filled with after Pa, then repeatedly two
It is secondary to vacuumize and be filled with high-purity argon gas operation, finally it will be evacuated to 5 × 10 in quartz ampoule-3Oxy-acetylene flame is utilized after Pa by external diameter
It is melting sealed for the quartz ampoule at 3~5mm；
5th, alloy cast ingot homogenization heat treatment
The sealed silica envelope that step 4 is obtained is placed in resistance furnace, 900 are warming up to 5~10 DEG C/min firing rate~
950 DEG C and 24~48h of insulation, insulation terminates rear furnace cooling to room temperature, obtains the alloy cast ingot of homogenization heat treatment；
6th, the preparation of micron alloying pellet
Cylinder of the alloy cast ingot that the homogenization that step 5 is obtained is heat-treated using Wire EDM into height for 8~10mm
Shape alloy cast ingot, cut surface is polished to remove cutting vestige with 320# sand paper, the cylindric alloy after polishing is then immersed third
Ultrasonic wave cleaning removes surface and oil contaminant in ketone solution, then cylindric alloy is put into drying box, in 60~80 DEG C of dryings
10min；
Dried cylindric alloy cast ingot is crushed, the cylindric alloy cast ingot of crushing is ground with agate mortar, so
Sieved afterwards with standard sample and the alloying pellet obtained after grinding is screened to obtain the alloying pellet that particle diameter is 38.5~710 μm, will
The alloying pellet that particle diameter is 38.5~710 μm is immersed in acetone soln, is cleaned by ultrasonic 5~10 minutes, last drying process produces
To micron alloying pellet；
7th, micron alloying pellet stress relief annealing is heat-treated
It is 9mm to take external diameter, wall thickness 1.5mm, long 300mm through hole quartz ampoule, and is cleaned and dried with the method for step 3,
First with oxy-acetylene flame by the end closure of quartz ampoule one, then its reduced diameter will be made extremely with oxy-acetylene flame melting at quartz ampoule 1/3 and 2/3
3mm, the micron alloying pellet that step 6 obtains is positioned over quartzy seal of tube one end, takes 100 μ m-thick Ti paper tinsels to be placed in quartz ampoule
At portion 1/2, wherein ensureing not contacting to prevent both from reacting at high temperature between micron alloying pellet and Ti paper tinsels；Then will
Quartz ampoule is evacuated to 0.5~5 × 10-30.1MPa high-purity argon gas is filled with after Pa, quartz ampoule is then evacuated to 0.5 again~
5×10-30.1MPa high-purity argon gas is filled with after Pa, quartz ampoule is finally evacuated to 0.5~5 × 10 again-3Pa, vacuumize
The external diameter that will be close to open at one end using oxy-acetylene flame simultaneously is melting sealed at the quartz ampoule at 3mm；
Quartz ampoule after sealing is put into high temperature resistance furnace, after being warming up to 450~550 DEG C with 5~10 DEG C/min of firing rates
20~24h is incubated, last quartz ampoule furnace cooling to room temperature, that is, completes the stress relief annealing heat treatment of micron alloying pellet；
8th, the preparation of hybrid microscale alloying pellet
The method of repeat step one to seven, repeat to change Ni every timexMnyGazThe value of middle x, y, z, ensure to repeat to obtain every time
Micron alloying pellet element ratio it is different, after the different micron alloying pellet of two or more element ratios is mixed, leaching
Entering in the container equipped with absolute ethyl alcohol, carry out mechanical agitation, mechanical agitation is ultrasonically treated simultaneously, after the completion of, remove container
Interior absolute ethyl alcohol, container is placed in drying box, is dried 10min at 60~80 DEG C, that is, is completed.
A kind of 2. preparation method of high refrigerating capacity nickel manganese gallium micron alloying pellet according to claim 1, it is characterised in that
The frequency for being cleaned by ultrasonic processing described in step 2 is 40kHz, power 300W.
A kind of 3. preparation method of high refrigerating capacity nickel manganese gallium micron alloying pellet according to claim 1, it is characterised in that
The thickness of Ti paper tinsels described in step 4 is 100 μm.
A kind of 4. preparation method of high refrigerating capacity nickel manganese gallium micron alloying pellet according to claim 1, it is characterised in that
It is the step of drying process described in step 6：In drying box 10min is dried at 60~80 DEG C.
A kind of 5. preparation method of high refrigerating capacity nickel manganese gallium micron alloying pellet according to claim 1, it is characterised in that
Dried cylindric alloy cast ingot is crushed described in step 6, the cylindric alloy cast ingot of crushing ground with agate mortar
Mill, then sieved with standard sample and the alloying pellet obtained after grinding is screened to obtain the alloy that particle diameter is 38.5~45 μm
Grain.
A kind of 6. preparation method of high refrigerating capacity nickel manganese gallium micron alloying pellet according to claim 1, it is characterised in that
It is the step of mechanical agitation described in step 8：Using the mechanical agitation oar matched with inside diameter of vessel, with 300 revs/min of stirrings of rotating speed
40min。
A kind of 7. preparation method of high refrigerating capacity nickel manganese gallium micron alloying pellet according to claim 1, it is characterised in that
It is the step of supersound process described in step 8：30 are ultrasonically treated in the supersonic generator that power is 300W, frequency is 40kHz
~40min.
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| WO2003093520A1 (en) * | 2002-04-27 | 2003-11-13 | Emerson Electric (China) Holdings Co. Ltd. | PROCESS FOR INCREASING MAGNETIC-FIELD-INDUCED STRAIN IN POLYCRYSTALLINE Ni2MnGa BY MAGNETIC HEAT TREATMENT |
| CN1584082A (en) * | 2004-06-09 | 2005-02-23 | 北京科技大学 | Compounds with large magnetic entropy changes and their preparation |
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| WO2003093520A1 (en) * | 2002-04-27 | 2003-11-13 | Emerson Electric (China) Holdings Co. Ltd. | PROCESS FOR INCREASING MAGNETIC-FIELD-INDUCED STRAIN IN POLYCRYSTALLINE Ni2MnGa BY MAGNETIC HEAT TREATMENT |
| CN1584082A (en) * | 2004-06-09 | 2005-02-23 | 北京科技大学 | Compounds with large magnetic entropy changes and their preparation |
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