CN100489137C - Rare earth-iron-silicon base compound having primary magnetic phase change characteristics and its preparation method - Google Patents
Rare earth-iron-silicon base compound having primary magnetic phase change characteristics and its preparation method Download PDFInfo
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- CN100489137C CN100489137C CNB2006100947863A CN200610094786A CN100489137C CN 100489137 C CN100489137 C CN 100489137C CN B2006100947863 A CNB2006100947863 A CN B2006100947863A CN 200610094786 A CN200610094786 A CN 200610094786A CN 100489137 C CN100489137 C CN 100489137C
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Abstract
The invention relates to a kind of compound of rare earth-Fe-silica base with primary magnetic phase-change and its preparation method. Its chemical formula is La1-xRxFe13-ySiyBzXalpha, in which R is one or combination of rare-earth element such as Nd, Ce, Pr, X is one or combination of H and N. The preparation method is as follows: After melting, powdered and banded materials with small scale are achieved by fast cooling. Then, they are carried with uniform heat treatment. X is added by hydrogenating (nitriding). Compounds in this invention all present primary magnetic phase-change. Its curie temperature can be controlled in 150-350K and has enormous magneto-caloric effect and magnetostriction. Preparation method can shorten synthetic time and prepare samples without alpha-Fe phase. It also has simple craft and low cost.
Description
Technical field
The present invention relates to rare earth-iron-silicon (R-Fe-Si) based compound, particularly have compound of primary magnetic phase change and preparation method thereof, this compound has huge magnetothermal effect and magnetostriction, can be used as magnetic refrigeration working substance and magnetostriction materials.
Background technology
Ferromagnetic material takes place near its Curie temperature, and ferromagnetic/paramagnetic changes, general this magnetic phase transition belongs to second-order phase transition, in the only a few material, also observed primary magnetic phase change characteristics, thereby these bill of material reveal special function, for example the huge magnetothermal effect that presses for of magnetic refrigeration and huge magnetostriction.
The mixture heat of La and Fe is difficult to form binary compound greater than zero, with then obtaining NaZn behind a small amount of Si or the alternative Fe of Al
13The pseudo-binary compound of type cubic structure.Up to the La that finds low Si content (Fe, Si)
13Present primary magnetic phase change characteristics (document 1., J.Appl.Phys., 1999,85 (1): 4756-4758.), and have huge magnetothermal effect (document 2.Appl.Phys.Lett., 2001,78:3675-3677.), this compounds is just paid close attention to, and is expected the magnetic refrigerating working material as a kind of high performance-price ratio, solves the too high problem of nearly room temperature magnetic refrigerating cost.After this, find that again this compound also has the ultra-magnetic telescopic effect, magnetostriction coefficient has surpassed (Tb, Dy) Fe
2(document 3.Appl.Phys.Lett., 2001,79:653-655), make this compound become the multifunctional novel material that the utmost point has application prospect.
La (Fe, Si)
13These performances of compound are relevant with its special magnetic phase transition, are included under the Curie temperature ferromagnetic/paramagnetic of taking place and paramagnetic/ferromagnetic primary magnetic phase change during a little more than Curie temperature, and only at low Si content (LaFe
13-xSi
xIn, x=1.4～1.6) compound in just can observe this class magnetic phase transition and huge magnetothermal effect and magnetostriction.
CN1140646C disclose a kind of La (Fe, Si)
13Compound, the Curie temperature with huge magnetic entropy compound when becoming are difficult to satisfy the service requirements in the wide temperature range more about 200K.By increase Si content or adding Co, H, N, the method for elements such as C can be brought up to Curie temperature near the room temperature, but the trend of impelling magnetic phase transition to be transformed to second-order phase transition by first-order phase transition is all arranged.CN1450190 disclose a kind of La with great magnetic entropy variation (Fe, Si)
13Based compound and preparation method thereof, but substitute partial L a with other heavy rare earths, when perhaps adding C, Curie temperature raises, with causing that then Curie temperature reduces behind the Mn replacement part Fe, but meanwhile magnetothermal effect declines to a great extent, and this is the result who causes the primary magnetic phase change forfeiture to cause owing to alloying.
La (Fe, Si)
13The resulting anomaly difficulty of based compound compound, the alloy pig of melting need be incubated tens of days down at 900～1100 ℃ and just can obtain near monophasic sample, can not eliminate fully mutually even so still have small portion of residual α-Fe, and its performance is had adverse influence.
In sum, for La (Fe, Si)
13Based compound, near its Curie temperature, have primary magnetic phase change characteristics and be and obtain huge magnetothermal effect and magnetostrictive prerequisite, the improvement by alloying and technology of preparing with the single phase property that guarantees product, shorten generated time and widen use temperature and become the problem that presses for solution.
Summary of the invention
--iron--silicon (R-Fe-Si) based compound and preparation method thereof that the object of the present invention is to provide rare earth, its composition is La
1-xR
xFe
13-ySi
yB
zX
α(atomic ratio) adopts melt rapid solidification and heat-treating methods to be prepared.This compounds has primary magnetic phase change characteristics (near the ferromagnetic/paramagnetic the Curie temperature changes and the itinerant electron metamagnetic transformation), and its Curie temperature can be adjusted in 150～350 ℃ of scopes by the method that changes alloying element content.The magnetothermal effect of compound and magnetostriction and LaFe
13-xSi
xH
y(x=1.4～1.6, H=0～2) compound is close, but generated time can shorten to 1～10 hour, and can obtain single-phase compound, remaining α-Fe phase basically eliminate.
The object of the present invention is achieved like this:
Consisting of of this compound: La
1-xR
xFe
13-ySi
yB
zX
α
Wherein, R is a kind of or its combination among rare earth Nd, Ce, the Pr, and X is a kind of of H and N or its combination.The scope of x is 0～0.5, and the scope of y is 1.2～1.6, and the scope of z is 0～0.7, and the scope of α is 0～2.
The compound that the present invention relates to can prepare by the method that describes below:
Purity is prepared according to said ratio above 99.9% metal La, R, Fe, Si and FeB master alloy, when adding R, can be adopted the mishmetal that meets proportioning.In order to replenish the scaling loss in the fusion process, should add rare earth into 5～10% weight.These raw materials melt and reach composition and evenly adopt the melt rapid cooling method to obtain the small scale material in the back, for example the method for available melt-spun is prepared into the strip that thickness is 1～100 μ m, perhaps obtains the rapid hardening powder that granularity is 1～100 μ m through atomizing fast.Under vacuum or the argon shield fast quenching thin strap or rapid hardening powder are cooled off after 1～10 hour fast in 800～1100 ℃ of insulations, do not contained the compound L a of X constituent element
1-xR
xFe
13-ySi
yB
zThe adding of X constituent element is changed processing by hydrogen (nitrogen) and is carried out, compound placed in hydrogen/argon-mixed atmosphere of 100～200 ℃ and keep carrying out in 0.5～2 hour hydrogenation, or 400～700 ℃ the nitrogenize of carrying out, hydrogen (nitrogen) content can be controlled by temperature, atmosphere hydrogeneous (nitrogen) amount and soaking time.
The invention has the beneficial effects as follows, can effectively eliminate remaining α-Fe phase, compound presents primary magnetic phase change characteristics (ferromagnetic/paramagnetic under the Curie temperature changes and the itinerant electron metamagnetic transformation during a little more than Curie temperature), Curie temperature can be controlled in 150～350K scope, and has huge magnetothermal effect and magnetostriction.Preparation method's technology of the present invention is simple, and generated time significantly shortens, and has reduced manufacturing cost.
Description of drawings
The present invention is further described below in conjunction with accompanying drawing.
Fig. 1 is the La of embodiment 1 preparation
0.7Nd
0.3Fe
11.6Si
1.4X-ray diffraction (XRD) figure;
Fig. 2 is the La of embodiment 1 preparation
0.7Nd
0.3Fe
11.6Si
1.4After the match lifting/lowering temperature curve outside 0.2T, wherein,
-■-expression La
0.7Nd
0.3Fe
11.6Si
1.4The specific magnetising moment varies with temperature the (curve of M-T) in temperature-rise period;
-△-expression La0.7Nd
0.3Fe
11.6Si
1.4The specific magnetising moment varies with temperature the (curve of M-T) in temperature-fall period;
Fig. 3 is the La of embodiment 1 preparation
0.7Nd
0.3Fe
11.6Si
1.4Near its Curie temperature isothermal magnetization curve, wherein,
-●-be illustrated in La under the magnetic field rising situation
0.7Nd
0.3Fe
11.6Si
1.4The isothermal magnetization curve;
-zero-be illustrated in La under the magnetic field reduction situation
0.7Nd
0.3Fe
11.6Si
1.4The isothermal magnetization curve;
Fig. 4 is the La of embodiment 1 preparation
0.7Nd
0.3Fe
11.6Si
1.4Near its Curie temperature Arrott figure, wherein,
-●-be illustrated in La under the magnetic field rising situation
0.7Nd
0.3Fe
11.6Si
1.4M
2-H/M curve;
-zero-be illustrated in La under the magnetic field reduction situation
0.7Nd
0.3Fe
11.6Si
1.4M
2-H/M curve;
When Fig. 5 is changed to 0～1T for foreign field, the La of embodiment 1 preparation
0.7Nd
0.3Fe
11.6Si
1.4Near its Curie temperature the magnetic entropy change and the relation curve of temperature (| Δ Sm|-T);
When Fig. 6 is changed to 0～1T for foreign field, the La of embodiment 2 preparations
0.7Nd
0.3Fe
11.6Si
1.4H
1.5Near its Curie temperature | Δ Sm|-T curve;
Fig. 7 is the LaFe of embodiment 3 preparations
11.6Si
1.4B
0.5XRD figure;
Fig. 8 is the LaFe of embodiment 3 preparations
11.6Si
1.4B
0.5After the match lifting/lowering temperature curve outside 0.2T, wherein,
-■-expression LaFe
11.6Si
1.4B
0.5M in temperature-rise period-T curve;
-△-expression LaFe
11.6Si
1.4B
0.5M in temperature-fall period-T curve;
Fig. 9 is the LaFe of embodiment 3 preparations
11.6Si
1.4B
0.5Near its Curie temperature isothermal magnetization curve, wherein,
-●-be illustrated in LaFe under the magnetic field rising situation
11.6Si
1.4B
0.5The isothermal magnetization curve;
-zero-be illustrated in LaFe under the magnetic field reduction situation
11.6Si
1.4B
0.5The isothermal magnetization curve;
Figure 10 is the LaFe of embodiment 3 preparations
11.6Si
1.4B
0.5Near its Curie temperature Arrott figure, wherein,
-●-be illustrated in LaFe under the magnetic field rising situation
11.6Si
1.4B
0.5M
2-H/M relation curve;
-zero-be illustrated in LaFe under the magnetic field reduction situation
11.6Si
1.4B
0.5M
2-H/M curve;
When Figure 11 is changed to 0～1T for foreign field, the LaFe of embodiment 3 preparations
11.6Si
1.4B
0.5Near its Curie temperature | Δ Sm|-T curve;
When Figure 12 is changed to 0～1T for foreign field, the LaFe of embodiment 4 preparations
11.6Si
1.4B
0.5H
1.5Near its Curie temperature | Δ Sm|-T curve.
Embodiment
With purity greater than 99.7% metal La, Nd, Fe and Si according to La
0.7Nd
0.3Fe
11.6Si
1.4(atomic ratio) prepared, and rare earth is added 8wt% to replenish scaling loss.Raw material is put into water jacketed copper crucible non-consumable arc-melting furnace, forvacuum to 2 * 10
-3Feed argon gas behind the Pa, obtain alloy cast ingot through arc melting.Ingot casting places in the silica tube of bottom opening, uses the high frequency electric source heat fused under argon shield, with certain pressure alloy melt is blown out to rotating on the copper roller then and obtains the fast quenching thin strap that thickness is about 23 μ m.Fast quenching thin strap is sealed in the silica tube that vacuumizes with behind the molybdenum sheet parcel, 1000 ℃ of insulations after 5 hours water-cooled make sample.The XRD figure spectrum of sample is seen Fig. 1, and sample is NaZn as seen from the figure
13The type cubic structure, but still have remaining α-Fe phase of about 6% through estimation, the LaFe that this and same procedure prepare
11.6Si
1.4Situation is identical.Carrying out magnetic property with Lakeshore 7300 vibrating sample magnetometers measures, under the 0.1T foreign field, (M-T) as shown in Figure 2, the Curie temperature that can obtain under the lifting/lowering temperature condition is respectively 185K and 181K to the specific magnetising moment (M) with the change curve of temperature (T) in the lifting/lowering temperature process.The specific magnetising moment has apparent in view thermal hysteresis, illustrates that the ferromagnetic/paramagnetic transformation that occurs under the Curie temperature belongs to first-order phase transition.Fig. 3 records La under 0～1T foreign field
0.7Nd
0.3Fe
11.6Si
1.4Near Curie temperature isothermal magnetization curve.On the curve from a little more than Curie temperature the time as can be seen, suddenly increasing appears in specific magnetising moment M after the match outside certain, this is the feature of foreign field inductive itinerant electron change magnetic transition (paramagnetic-ferromagnetic) just, the magnetic lag phenomenon occurs and fall a magnetzation curve, illustrates that this magnetic phase transition also belongs to first-order phase transition; Corresponding curve is the serpentine shape among the Arrott figure, has also provided strong evidence (Fig. 4).According to the Maxwell relational expression calculate that the magnetic entropy under the differing temps becomes near the Curie temperature (| Δ S
m|), the result is as shown in table 1.The relation curve of magnetic entropy change and temperature (| Δ S
m|-T) seen Fig. 5, as can be seen, reaches maximum at Curie temperature place magnetic entropy variate, La under the 1T foreign field
0.7Nd
0.3Fe
11.6Si
1.4Maximum magnetic entropy variable reached 14.5J/kg.K.LaFe with the same procedure preparation
11.6Si
1.4Compare La
0.7Nd
0.3Fe
11.6Si
1.4Curie temperature reduce about 9K, the magnetic entropy change then exceeds about 13%.
Method according to embodiment 1 prepares sample, and sample is carried out hydrogen treatment.
Hydrogen treatment is carried out in hydrogenation furnace, and the aforementioned compound that obtains places the interior maintenance of hydrogen/argon-mixed atmosphere of 160 ℃ 2 hours, and the atomic ratio that sucks hydrogen after measured in the compound is about 1.5.Fig. 6 is La
0.7Nd
0.3Fe
11.6Si
1.4H
1.5Near its Curie temperature magnetic entropy becomes the relation curve with temperature.As can be seen, the Curie temperature of this compound is 296K, and 1T after the match maximum magnetic entropy variable outward is 9.8J/kg.K.LaFe with the same procedure preparation
11.6Si
1.4H
1.5Compare La
0.7Nd
0.3Fe
11.6Si
1.4H
1.5Magnetic entropy become and then to exceed about 8%.
Embodiment 3 preparation LaFe
11.6Si
1.4B
0.5
According to LaFe
11.6Si
1.4B
0.5Composition prepare burden, the preparation method is substantially the same manner as Example 1, the thermal treatment soaking time of rapid tempering belt shortens to 2 hours, the gained sample is NaZn
13The type phase structure, its XRD figure spectrum is seen Fig. 7, and remaining α-Fe disappears mutually substantially, and the adding that B be described can promote the formation of 1:13 phase and stablize.The lifting/lowering temperature M-T curve of sample is seen Fig. 8, demonstrate one-level ferromagnetic/the paramagnetic phase change characteristics.Near the isothermal magnetization curve of Curie temperature and Arrott figure show the feature that itinerant electron becomes magnetic transition respectively as Fig. 9 and shown in Figure 10.Test and calculation result see Table in 1, | Δ S
m|-T relation curve as shown in figure 11, the Curie temperature of this compound is 190K, 1T after the match maximum magnetic entropy variable outward is 12.5J/kg.K, with the LaFe of same procedure preparation
11.6Si
1.4Approaching.
Method according to embodiment 3 prepares sample, and the hydrogen treatment through identical with embodiment 2 obtains LaFe
11.6Si
1.4B
0.5H
1.5Figure 12 is it | Δ S
m|-T relation curve, Curie temperature are 291K, and 1T after the match maximum magnetic entropy variable outward is 9.1J/kg.K, with the LaFe with the quadrat method preparation
11.6Si
1.4H
1.5Approaching.
Table 1.
| Embodiment | Form (atomic ratio) | Curie temperature T C(K) | The outer magnetic entropy after the match of 1T becomes | Δ S m|(J/kg.K) |
| 1 | La 0.7Nd 0.3Fe 11.6Si 1.4 | 185 | 14.5 |
| 2 | La 0.7Nd 0.3Fe 11.6Si 1.4H 1.5 | 296 | 9.8 |
| 3 | LaFe
11.6Si
1.4 |
190 | 12.5 |
| 4 | LaFe 11.6Si 1.4B 0.5H 1.5 | 291 | 9.1 |
| |
LaFe
11.6 |
194 | 12.7 |
| |
LaFe 11.6Si 1.4H 1.5 | 307 | 9.0 |
Claims (3)
1. rare earth-iron-silicon base compound with primary magnetic phase change characteristics, this compound also has huge magnetothermal effect and magnetostriction, it is characterized by:
This compound consist of La
1-xR
xFe
13-ySi
yB
zX
α,
Wherein, R is a kind of or its combination among rare earth Nd, Ce, the Pr, and X is H or N, and the scope of x is 0～0.5, and the scope of y is 1.2～1.6, and the scope of z is 0.5～0.7, and the scope of α is 0～2.
2. preparation method with rare earth-iron-silicon base compound of primary magnetic phase change characteristics as claimed in claim 1 is characterized by:
After the employing melting alloy melt is carried out rapid cooling method and obtain the small scale material, place then under vacuum or the gas shield condition and be incubated 1～10 hour, just can access the compound that does not contain the X constituent element at 800～1100 ℃; Obtain containing the compound of X constituent element by hydrogenation or nitriding treatment, hydrogen treatment by carrying out 100～200 ℃ of insulations in 0.5～2 hour, and nitriding treatment by carrying out 400～700 ℃ of insulations in 0.5～2 hour.
3. preparation method as claimed in claim 2 is characterized in that described rapid cooling method obtains the fast cold powder that granularity is 1～100 μ m for the method with melt-spun is prepared into strip or the quick atomizing of warp that thickness is 1～100 μ m.
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| CN100458986C (en) * | 2007-04-20 | 2009-02-04 | 北京科技大学 | Method for enhancing super-magnetostriction material performance |
| CN103639415B (en) * | 2013-12-11 | 2016-04-06 | 江苏大学 | The preparation method of a kind of high-performance rare-earth-iron-based magnetic cooling material |
| JP7038270B2 (en) * | 2015-10-30 | 2022-03-18 | テクニシエ ユニヴェルシテイト デルフト | Magnetic calorific material containing manganese, iron, silicon, phosphorus, and nitrogen |
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Non-Patent Citations (8)
| Title |
|---|
| La-Fe-M（M=Al,Si）化合物磁热性能研究进展. 肖素芬，陈云贵，吴金平等.中国稀土学报，第21卷第6期. 2003 |
| La-Fe-M(M=Al,Si)化合物磁热性能研究进展. 肖素芬，陈云贵，吴金平等.中国稀土学报，第21卷第6期. 2003 * |
| Large magnetic entropy change near room temperature intheLaFe11.5Si1.5H1.3 interstitial compound. Chen Yuan-Fu,Wang Fang,Shen Bao-Gen,etc.Chinese Physics,Vol.11 No.7. 2002 |
| Large magnetic entropy change near room temperature intheLaFe11.5Si1.5H1.3 interstitial compound. Chen Yuan-Fu,Wang Fang,Shen Bao-Gen,etc.Chinese Physics,Vol.11 No.7. 2002 * |
| 熔体快淬La1-xNdxFe11.5Si1.5(x=0,0.3,0.5)化合物磁性能和磁熵变. 吕伟鹏，谢鲲，杨森，宋晓平.稀有金属材料与工程，第35卷第1期. 2006 |
| 熔体快淬La1-xNdxFe11.5Si1.5(x=0,0.3,0.5)化合物磁性能和磁熵变. 吕伟鹏，谢鲲，杨森，宋晓平.稀有金属材料与工程，第35卷第1期. 2006 * |
| 熔体快淬LaFe11.5Si1.5的磁熵变. 谢鲲，宋晓平，吕伟鹏等.稀有金属材料与工程，第34卷第12期. 2005 |
| 熔体快淬LaFe11.5Si1.5的磁熵变. 谢鲲，宋晓平，吕伟鹏等.稀有金属材料与工程，第34卷第12期. 2005 * |
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