CN108486449B - 一种低热滞的MnNiGe基磁相变合金 - Google Patents
一种低热滞的MnNiGe基磁相变合金 Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 48
- 239000000956 alloy Substances 0.000 title claims abstract description 48
- 230000008859 change Effects 0.000 title claims abstract description 32
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 24
- 108010053481 Antifreeze Proteins Proteins 0.000 claims abstract description 9
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 238000010791 quenching Methods 0.000 claims abstract description 3
- 230000000171 quenching effect Effects 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000003723 Smelting Methods 0.000 abstract 2
- 238000000034 method Methods 0.000 abstract 1
- 230000007704 transition Effects 0.000 description 12
- 230000005415 magnetization Effects 0.000 description 8
- 229910000927 Ge alloy Inorganic materials 0.000 description 4
- 230000005294 ferromagnetic effect Effects 0.000 description 4
- 230000005298 paramagnetic effect Effects 0.000 description 4
- 229910006137 NiGe Inorganic materials 0.000 description 3
- 230000005290 antiferromagnetic effect Effects 0.000 description 3
- 238000010587 phase diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
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- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
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Abstract
本发明公开了一种低热滞的MnNiGe基磁相变合金，所述的磁相变合金原子表达式为Mn0.9Ni0.9Fe0.2Ge，其合金六角‑正交结构相变的热滞为5.3 K；所述磁相变合金以高纯金属单质Ni、Mn、Fe和Ge为原料，按照合金表达式精确配比各合金单质，通过电弧熔炼法制备，熔炼在高纯氩气氛围保护下进行；熔炼后的合金在800℃退火120小时，随后于冷水中淬火。该合金六角‑正交结构相变的热滞是同类合金中最低的，即将该体系结构相变温度降低到了现有最低水平。
Description
技术领域
本发明涉及一种低热滞的磁相变合金MnNiGe，属于相变合金制备领域。
背景技术
MnMX (M=Co，Ni；X=Ge，Si)合金普遍表现出温度诱导的结构相变，相变发生在六角母相和正交马氏体相之间。该相变伴随的热滞通常较大，一般高于20 K。较大的热滞不利于合金相变伴随效应的可逆发生。目前，该体系已报导的最低热滞为7 K。该值由中科院物理所在Mn1-xFexNiGe(x=0.11和0.18)合金中发现。在Mn1-xFexNiGe合金中，Fe替代Mn原子。
发明内容
本发明的目的是提供一种低热滞的磁相变合金MnNiGe。
实现本发明目的的技术解决方案是：
一种低热滞的磁相变合金MnNiGe，其合金表达式为Mn0.9Ni0.9Fe0.2Ge，所述合金六角-正交结构相变的热滞为5.3 K。
与现有技术相比，本发明的优点是：该合金六角-正交结构相变的热滞为5.3 K，是同类合金中最低的，即将该体系结构相变温度降低到了现有最低水平。
附图说明
图1是(MnNiGe)1-x (Fe2Ge) x 合金( 0.02≤ x ≤ 0.16 )的室温XRD衍射数据。
图2是5 T外磁场下(MnNiGe)1-x (Fe2Ge) x 合金( 0.02≤ x ≤ 0.16 )的磁化强度随温度的变化关系图。
图3是(MnNiGe)1-x (Fe2Ge) x 合金体系的磁性和结构相图。
图4是优选Mn0.9Ni0.9Fe0.2Ge合金在相变附近处的升场和降场的等温磁化曲线。
图5是优选Mn0.9Ni0.9Fe0.2Ge合金在不同外磁场下磁熵变随温度变化关系图。
具体实施方式
本发明在现有合金Mn1-xFexNiGe(x=0.11和0.18)基础上，利用Fe原子同时替代Mn和Ni原子，实现了热滞的进一步降低。
该合金的制备过程：以高纯（99.99%）金属单质Ni、Mn、Fe和Ge为原料，按照分子式Mn0.9Ni0.9Fe0.2Ge精确配比各合金单质。合金通过电弧熔炼制备，熔炼在高纯氩气氛围保护下进行。熔炼后的合金在800℃退火120小时，随后于冷水中淬火。
实施例：
利用X射线衍射仪（X-ray Diffraction：XRD）表征合金的物相结构。图1是(MnNiGe)1-x (Fe2Ge) x 合金( 0.02≤ x ≤ 0.16 )的室温XRD衍射数据，随着x的增加，体系室温结构逐渐由高温六角Ni2In型结构转变为低温正交TiNiSi型结构，这表明Fe2Ge的引入降低了合金的结构相变温度。
利用综合物性测量***（Physical Property Measurement System：PPMS）测量(MnNiGe)1-x (Fe2Ge) x 合金( 0.02≤ x ≤ 0.16 ) 等温磁化曲线和温度依赖的磁化强度。图2是5 T外场下(MnNiGe)1-x (Fe2Ge) x 合金( 0.02≤ x ≤ 0.16 )的磁化强度随温度变化的关系图。x = 0.02成分样品在380 K附近发生磁化强度的跳变，其对应的升温和降温曲线不重合，这表明体系经历结构相变，且该结构相变发生在顺磁态之间，当低于结构相变温度时，该成分样品又经历顺磁到反铁磁的转变，对应于MnNiGe合金的Néel转变。随着x的增加，合金的结构相变温度逐渐降低，且低温螺旋反铁磁结构将诱发形成铁磁态，二者的共同作用使得体系中实现了顺磁Ni2In型到铁磁TiNiSi型结构的磁结构转变，其中优选Mn0.9Ni0.9Fe0.2Ge合金的热滞仅为5.3 K，是所有这类相变合金中最低的。当x进一步增加，合金结构相变温度将低至高温Ni2In结构的居里温度以下，磁性转变和结构转变退耦合。对于x = 0.16样品，结构相变被抑制消失，图中仅能观察到顺磁到铁磁的居里转变。
图3是(MnNiGe)1-x (Fe2Ge) x 合金体系的磁性和结构相图。从该相图中可以看出，Fe2Ge引入能够在体系中构建从175 K到345 K宽约170 K的居里温度窗口，在该窗口的合金体系都实现了结构相变和磁性转变的耦合。其中Mn0.9Ni0.9Fe0.2Ge合金的热滞最低，仅为5.3K。
图4是优选Mn0.9Ni0.9Fe0.2Ge的等温磁化曲线。相变附近可以明显观察到磁场诱发的变磁性行为，且升场和降场伴随的磁滞表明该变磁性具有一级相变特征，对应于磁场诱发的结构相变。
图5是优选Mn0.9Ni0.9Fe0.2Ge的磁熵变随温度变化关系图。基于升场的等温磁化曲线，再利用Maxwell方程
获得该关系变化。从图中可以看出合金展现出明显的磁热效应，其中最大磁熵变值高达-40 J/(kg∙K)。
Claims (2)
1.一种低热滞的MnNiGe基磁相变合金，其特征在于，利用Fe原子同时替代Mn 和Ni原子，所述的磁相变合金原子表达式为 Mn0.9Ni0.9Fe0.2Ge，其合金六角-正交结构相变的热滞为5 .3 K。
2.如权利要求1所述的磁相变合金，其特征在于，所述磁相变合金以高纯金属单质Ni、Mn、Fe和Ge为原料，按照合金表达式精确配比各合金单质，通过电弧熔炼法制备，熔炼在高纯氩气氛围保护下进行；熔炼后的合金在800℃退火120小时，随后于冷水中淬火。
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3844775A (en) * | 1972-11-24 | 1974-10-29 | Du Pont | Polynary germanides and silicides |
| CN105154694A (zh) * | 2015-09-29 | 2015-12-16 | 南昌航空大学 | 通过电弧熔炼和铜模喷铸制备磁热材料Mn-Ni-Ge:Fe基系列合金棒材的方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3844775A (en) * | 1972-11-24 | 1974-10-29 | Du Pont | Polynary germanides and silicides |
| CN105154694A (zh) * | 2015-09-29 | 2015-12-16 | 南昌航空大学 | 通过电弧熔炼和铜模喷铸制备磁热材料Mn-Ni-Ge:Fe基系列合金棒材的方法 |
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