CN104923790B - A kind of gadolinium block materials and preparation method thereof - Google Patents
A kind of gadolinium block materials and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of gadolinium block materials and preparation method thereof.The preparation method includes following operating procedure：Step 1 is ground the raw material using mechanical attrition method using metal gadolinium powder as raw material；The nanoscale gadolinium powder is fitted into mold simultaneously precompressed by step 2 in the pretreatment chamber of argon gas protection；The mold is put into discharging plasma sintering equipment and is sintered by step 3, to obtain the gadolinium block materials.This method is simple and practicable, can prepare the gadolinium block materials of different grain sizes, and the average grain size of material is adjustable in 20 1000 nanometer ranges, and the corresponding magnetothermal effect of material increases with the grain size increase of the material of preparation within the scope of above-mentioned grain size.
Description
Technical field
The invention belongs to room temperature magnetic refrigerating technical fields, and in particular to a kind of gadolinium block materials and preparation method thereof.This hair
Bright method can prepare the gadolinium block materials of different grain sizes, to regulate and control the magnetothermal effect of gadolinium material.
Background technology
For the thulium of nanometer, since its scale reduces, the surface of material or the area of crystal boundary are drastically
Increase, thus it is made to show some new features in crystal structure, interface, thermodynamics, phase transformation etc., utilizes these new features
Final optics, electricity, magnetics, mechanics and the catalytic performance for improving material.
In recent years, room temperature magnetic refrigerating technology is because its is energy-efficient, non-environmental-pollution becomes current refrigeration technology due to the advantages that
The research hotspot in field is expected to become the magnetic Refrigeration Technique in room-temperature zone of new generation of substitution traditional gas compression refrigeration.And as magnetic
The development and application of the magnetic refrigerating working material of Refrigeration Technique key is by the pro-gaze of domestic and international researcher and attention and therefore takes
Obtained larger progress.Wherein, rare-earth element gadolinium (Gd) is because its Curie temperature (Tc=293.5K) is close to room temperature, and work temperature across
Greatly, (H under low magnetic field conditions<2T) adiabatic the advantages that temperature is got higher, thermal conductivity is good, easy processing, becomes currently the only applied to room temperature magnetic
The practical refrigeration working medium of refrigeration model machine.
And currently, regulating and controlling in terms of mainly carrying out ingredient to material to the research of the magnetothermal effect of material, to adjust material
The magnetothermal effect of material and Curie temperature, and it is less to study influence of the nanosizing of its micro-structure to its magnetothermal effect.
In addition, rare earth gadolinium element has great chemism, it is difficult to prepare as nano particle, if to be had
There are nanocrystalline block materials not only to need to effectively prevent oxidation it is also to be ensured that crystalline substance does not occur when being prepared into block materials for material
Grain length is big, therefore, it is big to prepare difficulty.
Invention content
For problems of the prior art, the purpose of the present invention is to provide a kind of gadolinium block materials and its preparation sides
Method.The method of the present invention is simple and practicable, can prepare the gadolinium block materials of different grain sizes, the average grain size of material exists
20-1000 nanometer ranges are adjustable, and within the scope of above-mentioned grain size material corresponding magnetothermal effect with preparation material
Grain size increases and increases.
To achieve the goals above, present invention employs following technical schemes：
A kind of preparation method of gadolinium block materials, including following operating procedure：
Step 1 is ground the raw material using mechanical attrition method using metal gadolinium powder as raw material；
Gadolinium powder after grinding is fitted into mold simultaneously precompressed by step 2 in the pretreatment chamber of argon gas protection；
The mold is put into discharging plasma sintering equipment and is sintered by step 3, to obtain the gadolinium block
Material.
In the above preparation method, the purity of the raw metal gadolinium powder is as a preferred implementation manner,
99.5% or more, granularity is 30-50 μm.It can be bought by commercial channel, be commercial product.
In the above preparation method, as a preferred implementation manner, in the mechanical attrition method, ratio of grinding media to material 10:
1-60:1 (such as 12:1、20:1、25:1、30:1、36:1、42:1、50:1、53:1、56:1、59:1), protective atmosphere 1-
Argon gas (Ar) atmosphere of 5bar (such as 2bar, 3bar, 4bar), rotational speed of ball-mill be 300-500rpm (such as 305rpm,
320rpm, 335rpm, 350rpm, 380rpm, 410rpm, 430rpm, 455rpm, 486rpm, 499rpm), Ball-milling Time 10-
50 hours (such as 11 hours, 15 hours, 23 hours, 28 hours, 35 hours, 40 hours, 45 hours, 49 hours).It is highly preferred that
In the mechanical attrition method, ratio of grinding media to material 10:1-30:1, protective atmosphere is argon gas (Ar) atmosphere of 4-5bar, rotational speed of ball-mill
For 400-500rpm, Ball-milling Time is 20-40 hours.
In the above preparation method, the oxygen concentration as a preferred implementation manner, in the pretreatment chamber is less than
0.5ppm (such as 0.5ppm, 0.4ppm, 0.1ppm, 0.05ppm).
In the above preparation method, the mold is sintered-carbide die as a preferred implementation manner, for example WC is hard
Matter mold.Die hard can bear bigger pressure with graphite jig.
In the above preparation method, as a preferred implementation manner, in the sintering, sintering temperature 300-800
DEG C (such as 310 DEG C, 340 DEG C, 370 DEG C, 390 DEG C, 450 DEG C, 490 DEG C, 540 DEG C, 580 DEG C, 640 DEG C, 690 DEG C, 730 DEG C, 740
℃、760℃、795℃).It is highly preferred that in the sintering, sintering temperature is 500-800 DEG C, pressure 100-2000MPa
(150MPa, 240MPa, 350MPa, 600MPa, 800MPa, 1200MPa, 1500MPa, 1800MPa, 1950MPa), heating rate
For 50-100 DEG C/min (55 DEG C/min, 68 DEG C/min, 80 DEG C/min, 90 DEG C/min, 98 DEG C/min), soaking time is 4-10 points
Clock (5min, 7min, 9min), and the sintering carries out under vacuum.Most preferably, in the sintering, sintering temperature
It it is 800 DEG C, pressure 1000MPa, heating rate is 50 DEG C/min, and soaking time is 5 minutes, vacuum degree 10-2Pa。
In the above preparation method, the average grain size of the gadolinium block materials is as a preferred implementation manner,
20-1000 nanometers.Within the scope of the grain size, the magnetothermal effect of the gadolinium block materials increases as grain size increases.
A kind of gadolinium block materials being prepared using the above method, the average grain size of the material are received for 20-1000
Rice (30nm, 50nm, 120nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 950nm) is pure
Degree reaches 99% or more, and theoretical density reaches 99.5% or more, is high-purity, high-compactness Gd block materials.
The present invention adds the method for discharge plasma sintering to be prepared for the Gd bulks of different grain sizes by high-energy ball-milling process
Material, the average grain size of prepared Gd block materials is adjustable in 20-1000 nanometer ranges, and the corresponding magnetic of material obtained
Fuel factor increases also with the grain size of the gadolinium block of material of preparation and is increased；That is pass through the grain size of adjusting gadolinium block of material
And the magnetothermal effect of controlled material.The maximum magnetic entropy variable of the Gd blocks of the present invention can reach 10.3JKg-1·K-1, it is a kind of very good
Magnetic refrigerating working material.
In addition, the present invention also has the characteristics that：1) preparation method of nanocrystalline Gd blocks of the invention, raw material are easy to get, and are
The material of common commercial, cost is relatively low, and preparation process is simple, easy to operate, it is easy to accomplish large-scale industrial production.2) anti-
It is environmentally safe without using noxious material in answering.3) surfactant, catalyst etc. need not be added in preparation process,
Impurity is seldom, is easy to get the product of high-purity.
Description of the drawings
Fig. 1 is shape appearance figure (the TEM photographs for the Gd block of material that high-energy ball-milling process adds prepared by the method for discharge plasma sintering
Piece)；
Fig. 2 is the adiabatic temperature varied curve (0-15000 oersteds) of Gd block of material prepared by embodiment 1；
Fig. 3 is the isothermal magnetization curve (M-H) (0-50000 oersteds) of Gd block of material prepared by embodiment 1；
Fig. 4 is that 2 high-energy ball-milling process of embodiment adds Gd block of material shape appearance figures prepared by the method for discharge plasma sintering
(TEM photos)；
Fig. 5 is the adiabatic temperature varied curve (0-15000 oersteds) of Gd block of material prepared by embodiment 2；
Fig. 6 is the isothermal magnetization curve (M-H) (0-50000 oersteds) of Gd block of material prepared by embodiment 2；
Fig. 7 is the adiabatic warm of the Gd block of material that 3 high-energy ball-milling process of embodiment adds prepared by the method for discharge plasma sintering
Spend varied curve (0-15000 oersteds).
Specific implementation mode
The raw metal gadolinium powder used in following embodiment is commercially available by commercial channel, and the purity of the raw material is
99.5%, granularity 30-50um.
Embodiment 1
The preparation method of Gd block of material 1：
(1) by 120 grams of (ratios of grinding media to material 30 of 4 grams of metal gadolinium powder raw material and stainless steel metal mill ball:1) it is put into togerther
In 250ml stainless-steel grinding tanks, and the argon gas (Ar) for being filled with 1bar is protected；Then the ball grinder of material sample will be installed i.e.
Above-mentioned grinding pot, which is placed on ball mill, carries out ball milling, ball milling condition：Rotational speed of ball-mill is 400rpm, and Ball-milling Time is 40 hours；
(2) pretreatment chamber (oxygen concentration 0.4ppm) protected in high-purity argon gas (purity reaches 99.99% or more), will grind
Gadolinium powder after mill is fitted into WC sintered-carbide dies, then the precompressed under 2Mpa pressure；
(3) mold equipped with gadolinium powder is put into discharge plasma sintering (Spark Plasma Sintering, abbreviation
SPS) sintered into metal gadolinium block materials in equipment (model SPS-5.40-IV/ET).Sintering process is：Vacuum degree is kept
It is 10-2Pa, 300 DEG C, sintering pressure 100MPa of sintering temperature, heating rate are 50 DEG C/min, and soaking time is 5 minutes.
The mean grain size for the sintered sample metal gadolinium block that 300 DEG C of the present embodiment SPS is obtained is 30 nanometers, referring to figure
1.Purity is 99.1% or more, and theoretical density reaches 99.6%.
Magnetic heating performance test is carried out to metal gadolinium Gd block materials samples manufactured in the present embodiment, test result is referring to table 1.
The specific test method is as follows：
Adiabatic temperature varied curve (Δ Tad-T)：
Using XHY type intelligence magnetothermal effect measuring instruments measure 250K of the gadolinium block under 15000 oersted of externally-applied magnetic field~
Adiabatic temperature varied curve (Δ T between 315Kad-T)。
Isothermal magnetization curve (M-H)：
The nanocrystalline gadolinium block sample of embodiment preparation is measured in difference using PPMS (multi-functional physical testing system)
At temperature (T) (between 270K~310K), changes of magnetic field (H) is the isothermal magnetization curve (M- under the conditions of (0-50000 oersteds)
H)。
As can be known from Fig. 2, the maximum adiabatic temperature of metal gadolinium Gd block materials manufactured in the present embodiment changes (Δ Tad) be
1.0K, meanwhile, corresponding Curie temperature is probably in 287K or so.
Max is combined to tie up equation by Fig. 3 isothermal magnetizations curve (M-H)Calculate gadolinium block
Maximum magnetic entropy variable (Δ SM) it is 4.2JKg-1·K-1。
Embodiment 2
The preparation method of Gd block of material 2：
(1) by 200 grams of (ratios of grinding media to material 50 of 4 grams of metal gadolinium powder raw material and stainless steel metal mill ball:1) it is put into togerther
In 250ml stainless-steel grinding tanks, and the argon gas (Ar) for being filled with 3bar is protected；Then the ball grinder of material sample will be installed i.e.
Above-mentioned grinding pot, which is placed on ball mill, carries out ball milling, ball milling condition：Rotational speed of ball-mill is 500rpm, and Ball-milling Time is 60 hours；
(2) pretreatment chamber (oxygen concentration 0.3ppm) protected in high-purity argon gas (purity reaches 99.99% or more), will grind
Gadolinium powder after mill is fitted into WC sintered-carbide dies, then the precompressed under 2Mpa pressure；
(3) mold equipped with gadolinium powder is put into discharge plasma sintering (Spark Plasma Sintering, abbreviation
SPS) sintered into metal gadolinium block materials in equipment (model SPS-5.40-IV/ET).Sintering process is：Vacuum degree is kept
It is 10-2Pa, 500 DEG C, sintering pressure 500MPa of sintering temperature, heating rate are 100 DEG C/min, and soaking time is 5 minutes.
The mean grain size for the sintered sample metal gadolinium block that 500 DEG C of the present embodiment SPS is obtained is 100 nanometers, referring to figure
4.Purity is 99.3%, and theoretical density reaches 99.7%.
Magnetic heating performance test is carried out to metal gadolinium Gd block materials samples manufactured in the present embodiment, test result is referring to table 1.
The specific test method is as follows with embodiment 1.
As can be known from Fig. 5, the maximum adiabatic temperature of metal gadolinium Gd block materials manufactured in the present embodiment changes (Δ Tad) be
1.9K, meanwhile, corresponding Curie temperature is probably in 291K or so.
Max is combined to tie up equation by Fig. 6 isothermal magnetizations curve (M-H)Calculate gadolinium block
Maximum magnetic entropy variable 7.7JKg-1·K-1。
Embodiment 3
The preparation method of Gd block of material 3：
(1) by 240 grams of (ratios of grinding media to material 60 of 4 grams of metal gadolinium powder raw material and stainless steel metal mill ball:1) it is put into togerther
In 250ml stainless-steel grinding tanks, and the argon gas (Ar) for being filled with 3bar is protected；Then the ball grinder of material sample will be installed i.e.
Above-mentioned grinding pot, which is placed on ball mill, carries out ball milling, ball milling condition：Rotational speed of ball-mill is 300rpm, and Ball-milling Time is 20 hours；
(2) pretreatment chamber (oxygen concentration 0.3ppm) protected in high-purity argon gas (purity reaches 99.99% or more), will grind
Gadolinium powder after mill is fitted into WC sintered-carbide dies, then the precompressed under 2Mpa pressure；
(3) mold equipped with gadolinium powder is put into discharge plasma sintering (Spark Plasma Sintering, abbreviation
SPS) sintered into metal gadolinium block materials in equipment (model SPS-5.40-IV/ET).Sintering process is：Vacuum degree is kept
It is 10-2Pa, 800 DEG C, sintering pressure 1000MPa of sintering temperature, heating rate are 50 DEG C/min, and soaking time is 5 minutes.
The grain size for the sintered sample metal gadolinium block that 800 DEG C of the present embodiment SPS is obtained is 1000 nanometers.Purity is
99.5%, theoretical density reaches 99.5%.
Magnetic heating performance test is carried out to metal gadolinium Gd block materials samples manufactured in the present embodiment, test result is referring to table 1.
The specific test method is as follows with embodiment 1.
As can be known from Fig. 7, the maximum adiabatic temperature of metal gadolinium Gd block materials manufactured in the present embodiment changes (Δ Tad) be
3.4K, meanwhile, corresponding Curie temperature is probably in 292.5K or so.
Max is combined to tie up equation by warm magnetization curve (M-H)Calculate the maximum of gadolinium block
Magnetic entropy becomes 10.3JKg-1·K-1。
The maximum thermal insulation Wen Bianyu Curie temperature of Gd blocks prepared by 1 embodiment 1-3 of table
Embodiment 4-7
Embodiment 4-7 prepares Gd block of material 4-7 respectively, and preparation method is as follows：
In addition to the sintering temperature in step (3) is different from embodiment 2, other techniques are same as Example 2.Embodiment 4-
The adiabatic temperature change of maximum, Curie temperature and the maximum magnetic entropy for the Gd blocks that 7 sintering temperature is obtained referring to table 2, this four embodiments
Become referring to table 2.
The magnetic heating performance of Gd blocks prepared by 2 embodiment 4-7 of table
Embodiment 8-10
Embodiment 8-10 prepares Gd block of material 8-10 respectively, and preparation method is as follows：
In addition to the ratio of grinding media to material in step (1) is different from embodiment 2, other techniques are same as Example 2.Embodiment 8-10
Ratio of grinding media to material referring to table 3, the adiabatic temperature of maximum of Gd blocks that these three embodiments obtain becomes, Curie temperature and maximum magnetic entropy variable ginseng
It is shown in Table 3.
The magnetic heating performance of Gd blocks prepared by 3 embodiment 8-10 of table
Claims (8)
1. a kind of preparation method of gadolinium block materials, which is characterized in that including following operating procedure：
Step 1 is ground the raw material using mechanical attrition method using metal gadolinium powder as raw material；
Gadolinium powder after grinding is fitted into mold simultaneously precompressed by step 2 in the pretreatment chamber of argon gas protection；
The mold is put into discharging plasma sintering equipment and is sintered by step 3, to obtain the gadolinium block materials；
Wherein,
In the mechanical attrition method, ratio of grinding media to material 10:1-60:1, protective atmosphere is the argon gas atmosphere of 1-5bar, rotational speed of ball-mill
For 300-500rpm, Ball-milling Time is 10-50 hours；
In the sintering, sintering temperature be 500-800 DEG C, pressure 100-2000MPa, heating rate be 50-100 DEG C/
Min, soaking time are 4-10 minutes, and the sintering carries out under vacuum.
2. preparation method according to claim 1, which is characterized in that the purity of the raw metal gadolinium powder is 99.5%
More than, granularity is 30-50 μm.
3. preparation method according to claim 1, which is characterized in that in the mechanical attrition method, ratio of grinding media to material 10:1-
30:1, protective atmosphere is the argon gas atmosphere of 4-5bar, and rotational speed of ball-mill 400-500rpm, Ball-milling Time is 20-40 hours.
4. preparation method according to claim 1, which is characterized in that the oxygen concentration in the pretreatment chamber is less than
0.5ppm。
5. preparation method according to claim 1, which is characterized in that the mold is sintered-carbide die.
6. preparation method according to claim 1, which is characterized in that in the sintering, sintering temperature is 800 DEG C, pressure
Power is 1000MPa, and heating rate is 50 DEG C/min, and soaking time is 5 minutes, vacuum degree 10-2Pa。
7. preparation method according to claim 1, which is characterized in that the average grain size of the gadolinium block materials is
100-1000 nanometers.
8. a kind of gadolinium block materials being prepared using claim 1-7 either method, which is characterized in that the material is averaged
Crystallite dimension is 100-1000 nanometers, and purity reaches 99% or more, and theoretical density reaches 99.5% or more.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1026279A1 (en) * | 1998-07-29 | 2000-08-09 | Dowa Mining Co., Ltd. | Permanent magnetic alloy with excellent heat resistance and process for producing the same |
| CN1804066A (en) * | 2005-12-23 | 2006-07-19 | 上海大学 | Method for preparing room temperature magnetic refrigerating working material Gd5Si2Ge2 |
| CN101549405A (en) * | 2009-05-19 | 2009-10-07 | 燕山大学 | High-pressure sintering preparation method of high-densification high-performance nano crystal block thermoelectric material |
| CN101786163A (en) * | 2010-02-09 | 2010-07-28 | 江苏大学 | Preparation method of high-performance room-temperature magnetic refrigeration nano bulk material |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100431748C (en) * | 2005-07-27 | 2008-11-12 | 北京工业大学 | Rare-earth element gadolinium nano particle and nano crystal block material preparing method |
| CN1743103A (en) * | 2005-08-05 | 2006-03-08 | 北京工业大学 | Rear-earth nano granule and nano crystal material preparing method and apparatus |
| CN100386337C (en) * | 2006-01-24 | 2008-05-07 | 北京工业大学 | Method for in-situ synthesizing preparation of high-purity GdH2 block material |
| US9212409B2 (en) * | 2012-01-18 | 2015-12-15 | Cook Medical Technologies Llc | Mixture of powders for preparing a sintered nickel-titanium-rare earth metal (Ni-Ti-RE) alloy |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1026279A1 (en) * | 1998-07-29 | 2000-08-09 | Dowa Mining Co., Ltd. | Permanent magnetic alloy with excellent heat resistance and process for producing the same |
| CN1804066A (en) * | 2005-12-23 | 2006-07-19 | 上海大学 | Method for preparing room temperature magnetic refrigerating working material Gd5Si2Ge2 |
| CN101549405A (en) * | 2009-05-19 | 2009-10-07 | 燕山大学 | High-pressure sintering preparation method of high-densification high-performance nano crystal block thermoelectric material |
| CN101786163A (en) * | 2010-02-09 | 2010-07-28 | 江苏大学 | Preparation method of high-performance room-temperature magnetic refrigeration nano bulk material |
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