CN102712543A - 磁热材料 - Google Patents
磁热材料 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 58
- 238000001816 cooling Methods 0.000 claims description 28
- 238000005245 sintering Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 230000004927 fusion Effects 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 229910045601 alloy Inorganic materials 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 12
- 238000007669 thermal treatment Methods 0.000 claims description 12
- 238000004528 spin coating Methods 0.000 claims description 9
- 238000010791 quenching Methods 0.000 claims description 8
- 230000000171 quenching effect Effects 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 5
- 239000007790 solid phase Substances 0.000 claims description 5
- 229910052729 chemical element Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 230000005291 magnetic effect Effects 0.000 description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 230000000694 effects Effects 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 6
- 238000003746 solid phase reaction Methods 0.000 description 5
- 238000010671 solid-state reaction Methods 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910000906 Bronze Inorganic materials 0.000 description 3
- 239000010974 bronze Substances 0.000 description 3
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000005415 magnetization Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000009702 powder compression Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 241000238366 Cephalopoda Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 206010027336 Menstruation delayed Diseases 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010099 solid forming Methods 0.000 description 1
- 230000035924 thermogenesis Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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Abstract
描述了通式(MnxFe1-x)2+zP1-ySiy的磁热材料，其中0.55≤x<1，0.4≤y≤0.8，-0.1≤z≤0.1。
Description
本发明涉及多晶磁热材料，其制备方法及其在冷却器、换热器或热发生器，尤其是制冷机中的用途。
热磁材料(也称为磁热材料)可用于冷却，例如用于制冷机或空调装置中、用于热泵中或者用于由热直接产生功率而无需转化成机械能的中间步骤。
这类材料原则上是已知的且例如描述于WO2004/068512中。磁性冷却技术基于磁热效应(MCE)且可为已知蒸气循环冷却方法的替代方案。在具有磁热效应的材料中，由外部磁场所导致的无规取向磁矩的取向使该材料发热。该热量可通过传热从该MCE材料中移出至四周大气中。当此后关闭或移除磁场时，磁矩回复成无规排布状态，这导致该材料冷却至低于环境温度。这种效应可用于冷却目的。通常将传热介质如水用于从所述磁热材料中移除热量。
用于热磁发生器中的材料同样基于磁热效应。在具有磁热效应的材料中，由外部磁场所导致的无规取向磁矩的取向导致该材料发热。该热量可由所述MCE材料通过传热释放至四周大气中。当此后关闭或移除磁场时，磁矩回复成无规取向状态，这导致该材料冷却至低于环境温度。这种效应首先可用于冷却目的，其次可用于将热量转化成电能。
磁热产生电能与磁发热和冷却有关。首次将所述产生能量的方法称为热磁能量产生方法。与Peltier或Seebeck型设备相比，这些磁热设备可具有显著更高的能量效率。
该物理现象的研究始于19世纪晚期，其时两个科学家Tesla和Edison提交了与热磁发生器有关的专利。在1984年，Kirol描述了许多可能的应用且对其热力学进行了分析。此时，认为钆是用于室温附近的应用场合中的潜在材料。
热磁电发生器例如由N.Tesla描述于US428,057中。据称铁或其他磁性物质的磁性能由于加热至特定温度而可部分或完全破坏或者可消失。在冷却过程中，重新获得磁性能并回复至起始状态。该效应可用于产生电功率。当将导电体暴露于交变磁场中时，磁场的变化导致在该导体中产生感应电流。例如，当磁性材料被线圈围绕，然后在永久磁场中加热，其后进行冷却时，在每种情况下在加热和冷却过程中在所述线圈中产生感应电流。这能将热能转化成电能而无需中间转化成机械功。在Tesla所描述的方法中，通过烘箱或密闭式壁炉加热作为磁性材料的铁，然后再次冷却。
对热磁或磁热应用而言，所述材料应允许有效地换热，从而能获得高效率。在冷却和产生功率这两个过程中，将热磁材料用于换热器中。
WO2004/068512公开了通式MnFe(PwGexSiz)的磁热材料。优选的材料为MnFeP0.45-0.70Ge0.55-0.30或MnFeP0.5-0.70(Si/Ge)0.5-0.30。在每种情况下，实施例组合物包含一定比例的Ge。这些材料仍不具有适于所有应用的足够大的磁热效应。
本发明的目的是提供具有大磁热效应的磁热材料。
根据本发明，所述目的通过如下通式的磁热材料实现：
(MnxFe1-x)2+zP1-ySiy
其中
0.55≤x<1，
0.4≤y≤0.8，
-0.1≤z≤0.1。
x的最大值优选为0.57，更优选为0.6。x的最大值优选为0.99，特别为0.9，尤其为0.85。例如，x的最大值为0.8，特别为0.65。更优选0.57≤x≤0.8，尤其为0.6≤x≤0.65。
y的最大值优选为0.45，更优选为0.5，尤其为0.51。y的最大值优选为0.7，更优选为0.6。更优选0.45≤y≤0.7，特别地0.5≤y≤0.6，尤其是0.51≤y≤0.6。
z可与0相差较小值。优选-0.05≤z≤0.05，特别地-0.02≤z≤0.02，尤其是z=0。
本发明磁热材料优选具有Fe2P型六方结构。
根据本发明，已发现尤其是Mn/Fe元素比大于1.2使磁热材料能形成稳定的相且具有低热磁滞。
本发明材料能在-50℃至+100℃的应用温度下工作。
本发明材料的磁热效应与称为巨磁热材料的那些如MnFePxAs1-x、Gd5(Si,Ge)4或La(Fe,Si)13的磁热效应相当。
在1T磁场中在1℃/分钟扫描速率下测得的热磁滞优选<2℃。
本发明材料额外具有如下优点：其由大量可得且通常归类为无毒的元素形成。
根据本发明使用的热磁材料可以以任何合适的方式制备。
本发明磁热材料可通过该材料的起始元素或起始合金的固相转化或液相转化，随后冷却，然后压制、在惰性气氛下烧结并热处理，随后冷却至室温而制备，或者可通过起始元素或起始合金的熔体的熔融旋涂制备。
例如，所述热磁材料通过在球磨机中使该材料的起始元素或起始合金发生固相反应，随后压制、在惰性气氛下烧结并热处理，随后冷却(例如缓慢冷却)至室温而制备。该方法例如描述于J.Appl.Phys.99，2006，08Q107中。
例如，可将呈元素形式或者呈初级合金如Mn2P或Fe2P形式的合适量Mn、Fe、P和Si在球磨机中研磨。将该粉末压制并在保护性气氛下，在900-1300℃，优选约1100℃的温度下烧结合适的时间，优选1-5小时，尤其为约2小时，然后在700-1000℃，优选约850℃的温度下热处理合适的时间，例如1-100小时，更优选10-30小时，尤其为约20小时。
或者，可将元素粉末或初级合金粉末在感应炉中一起熔融。然后又可如上所述进行热处理。
也可通过熔融旋涂加工。这可获得更为均匀的元素分布，从而获得改善的磁热效应；参见Rare Metals，第25卷，2006年10月，第544-549页。在其中所述的方法中，首先使起始元素在氩气气氛下感应熔融，然后通过喷嘴以熔融状态喷涂至旋转铜辊上。随后在1000℃下烧结并缓慢冷却至室温。此外，所述制备还可参见WO2004/068512和PCT/EP2009/055024。
因此，优选一种制备所述热磁材料的方法，包括如下步骤：
a)使呈固相和/或液相的化学元素和/或合金以对应于所述磁热材料的化学计量量转化；
b)任选将获自步骤a)的反应产物转化成固体；
c)对获自步骤a)或b)的固体进行烧结和/或热处理；
d)将获自步骤c)的烧结和/或热处理的固体以至少100K/s的冷却速率骤冷。
当在烧结和/或热处理之后，不将该金属基材料缓慢冷却至环境温度，而是以高冷却速率骤冷时，可显著降低热磁滞，且可获得大的磁热效应。该冷却速率为至少100K/s。冷却速率优选为100-10000K/s，更优选为200-1300K/s。尤其优选冷却速率为300-1000K/s。
骤冷可通过任何合适的冷却方法实现，例如用水或含水液体如冷却的水或冰和/或水混合物骤冷所述固体。可使所述固体例如降落进冰冷却的水中。也可用过冷气体如液氮骤冷所述固体。其他骤冷方法是本领域技术人员所已知的。此时有利地是受控和快速冷却。
所述热磁材料制备的其余步骤不那么重要，只要最后一步包括以本发明冷却速率骤冷所述烧结和/或热处理的固体即可。所述方法可用于制备任何合适的上述热磁材料。
在所述方法的步骤(a)中，使呈固相或液相的存在于随后的热磁材料中的元素和/或合金以对应于所述热磁材料的化学计量量转化。
优选通过将所述元素和/或合金在密闭容器或挤压机中混合加热或者通过在球磨机中进行固相反应而实施步骤a)的反应。特别优选实施固相反应，所述固相反应尤其是在球磨机中进行。该反应原则上是已知的；参见上述引用文献。通常将存在于随后热磁材料中的单独元素的粉末或者两种或更多种单独元素的合金的粉末以粉末形式以合适重量比例混合。如果需要的话，可额外对所述混合物进行研磨以获得微晶粉末混合物。优选在球磨机中加热该粉末混合物，这导致其进一步粉碎，此外还获得良好的混合，并导致在该粉末混合物中发生固相反应。或者，将单独元素以粉末形式以所选化学计量量混合，然后熔融。
在密闭容器中混合加热能使挥发性元素固定并控制化学计量量。在使用磷的情况下尤其如此，磷在开放式系统中容易蒸发。
在所述反应之后，对所述固体进行烧结和/或热处理，其可具有一个或多个中间步骤。例如，可将步骤a)中所得的固体成型，然后将其烧结和/或热处理。
或者，可将获自球磨机的固体送至熔融旋涂工艺。熔融旋涂工艺本身是已知的且例如描述于Rare Metals，第25卷，2006年10月，第544-549页以及WO2004/068512和PCT/EP2009/055024中。
在这些方法中，将步骤a)中所得的组合物熔融并喷涂至旋转的冷金属辊上。该喷涂可通过提高喷嘴上游压力或降低喷嘴下游压力而实现。通常使用旋转铜鼓或辊，合适的话可额外对其进行冷却。铜鼓优选以10-40m/s，尤其为20-30m/s的表面速率旋转。在铜鼓上，所述液体组合物以优选为102-107K/s的速率，更优选以至少104K/s的速率，尤其以0.5-2×106K/s的速率冷却。
所述熔融旋涂如步骤a)中的反应一样也可在减压下或在惰性气氛下进行。
熔融旋涂获得高加工速率，这是因为可缩短随后的烧结和热处理时间。因此，尤其是在工业规模上，所述热磁材料的制备在经济上更显著可行。喷雾干燥也获得高加工速率。特别优选实施熔融旋涂。
或者，在步骤b)中可进行喷雾冷却，其中将获自步骤a)的组合物的熔体喷雾至喷雾塔中。所述喷雾塔例如可额外冷却。在喷雾塔中，通常获得103-105K/s，尤其为约104K/s的冷却速率。
如上所述在步骤c)中对所述固体进行烧结和/或热处理。
在使用熔融旋涂方法的情况下，可显著缩短烧结或热处理时间，例如缩短至5分钟至5小时，优选10分钟至1小时。与为10小时烧结和50小时热处理的其他常规值相比，这具有巨大的时间优势。
所述烧结/热处理导致颗粒边界部分熔融，以使得所述材料进一步密实。
因此，步骤b)中的熔融和快速冷却使步骤c)的时间显著减少。这也允许连续制备所述热磁材料。
本发明磁热材料可用于任何合适的应用场合。例如，其用于冷却器、换热器或热发生器中。特别优选用于制冷机中。
通过实施例详细阐述本发明。
实施例
制备磁热材料
将Mn1.2Fe0.8P0.4Si0.6标称化学计量量的Mn薄片、Si薄片和Fe2P粉末的15g混合物在BPR(球与粉末重量比)为4的行星式球磨机中研磨10小时。然后将在研磨中获得的粉末压制成圆柱状，并密封于处于200毫巴氩气下的安瓿中。在此之后为在1100℃下烧结2小时和在850℃热处理20小时的步骤。在炉冷却后取出试样。
以此方式制备具有Mn1.24Fe0.76P0.44Si0.56、Mn1.24Fe0.76P0.46Si0.54、Mn1.28Fe0.72P0.48Si0.52和Mn1.3Fe0.7P0.5Si0.5标称组成的试样。
磁性能
在Quantum Design MPMSXL SQUID磁强计中测定如此制备的试样的磁性能。
图1显示了磁化(Am2kg-1)的温度依赖性，所述磁化在1T磁场中以1K/分钟扫描速率测定。在加热和冷却曲线之间相变处的温度依赖性显示这些试样具有一级磁相变的热磁滞。该值依赖于具体试样，但在所研究的试样中总是低于2K。在所述曲线中，由朝上箭头指示的曲线与所述试样的冷却有关，且由向下箭头指示的曲线与所述试样的加热有关。由于急剧磁相变所导致的约100Am2kg-1区域内的显著磁化变化表明具有大的磁热效应。
图2显示了作为温度函数的这些试样的磁熵变(J/kg K)。磁熵变使用麦克斯韦方程由磁等温线(例如参见图3)计算，所述磁等温线在不同温度下在接近相变处测定。所得磁熵变值与所谓的GMCE(巨磁热效应材料)的相应值相当。
空心符号与0-1T的磁场变化有关。实心符号表示0-2T的磁场变化。
图3显示了Mn1.2Fe0.8P0.4Si0.6在接近磁相变处的磁等温线(Am2/kg)。
Claims (9)
1.一种如下通式的磁热材料：
(MnxFe1-x)2+zP1-ySiy
其中
0.55≤x<1，
0.4≤y≤0.8，
-0.1≤z≤0.1。
2.根据权利要求1的磁热材料，其中0.57≤x≤0.8。
3.根据权利要求1或2的磁热材料，其中0.45≤y≤0.7。
4.根据权利要求1-3中任一项的磁热材料，其中-0.05≤z≤0.05。
5.根据权利要求1-4中任一项的磁热材料，其具有Fe2P型六方结构。
6.一种制备根据权利要求1-5中任一项的磁热材料的方法，包括使所述材料的起始元素或起始合金固相转化或液相转化，任选冷却，然后压制，在惰性气氛下烧结并热处理，随后冷却至室温；或者包括对所述起始元素或起始合金的熔体进行熔融旋涂。
7.根据权利要求6的方法，包括如下步骤：
a)使呈固相和/或液相的化学元素和/或合金以对应于所述磁热材料的化学计量量转化；
b)任选将获自步骤a)的反应产物转化成固体；
c)对获自步骤a)或b)的固体进行烧结和/或热处理；
d)将获自步骤c)的烧结和/或热处理的固体以至少100K/s的冷却速率骤冷。
8.根据权利要求1-5中任一项的磁热材料在冷却器、换热器或热发生器中的用途。
9.根据权利要求8的用途，用于制冷机中。
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| CN105684106A (zh) * | 2013-08-09 | 2016-06-15 | 巴斯夫欧洲公司 | 含b的磁热材料 |
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| AU2011225713A1 (en) * | 2010-03-11 | 2012-08-23 | Basf Se | Magnetocaloric materials |
| JP6009994B2 (ja) * | 2012-06-12 | 2016-10-19 | 国立大学法人九州大学 | 磁気冷凍材料 |
| US9245673B2 (en) | 2013-01-24 | 2016-01-26 | Basf Se | Performance improvement of magnetocaloric cascades through optimized material arrangement |
| CN103205590B (zh) * | 2013-04-27 | 2015-01-07 | 北京工业大学 | 磁制冷材料的一种制备工艺 |
| JP2016520256A (ja) | 2013-05-08 | 2016-07-11 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | 磁気冷却装置用の回転磁気遮蔽システムの使用方法 |
| US9887027B2 (en) | 2013-09-27 | 2018-02-06 | Basf Se | Corrosion inhibitors for Fe2P structure magnetocaloric materials in water |
| CA2958198A1 (en) * | 2014-07-18 | 2016-01-21 | Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College | Multicaloric mnnisi alloys |
| JP7038270B2 (ja) * | 2015-10-30 | 2022-03-18 | テクニシエ ユニヴェルシテイト デルフト | マンガン、鉄、ケイ素、リン、及び窒素を含む磁気熱量材料 |
| EP3469606B8 (en) | 2016-06-10 | 2021-06-23 | Technische Universiteit Delft | Magnetocaloric materials comprising manganese, iron, silicon, phosphorus and carbon |
| CN109791825A (zh) | 2016-08-31 | 2019-05-21 | 巴斯夫欧洲公司 | 磁热材料参数的受控变化 |
| WO2018060217A1 (en) | 2016-09-29 | 2018-04-05 | Basf Se | MAGNETOCALORIC MATERIALS COMPRISING Mn, Fe, ONE OR BOTH OF Ni AND Co, P, Si AND B |
| WO2018197612A1 (en) | 2017-04-27 | 2018-11-01 | Basf Se | Preparation of powders of nitrided inorganic materials |
| WO2019121766A1 (en) | 2017-12-18 | 2019-06-27 | Basf Se | Building unit for magnetocaloric heat exchanger |
| KR102069770B1 (ko) | 2018-06-07 | 2020-01-23 | 한국생산기술연구원 | 자기열량합금 및 이의 제조 방법 |
| EP3980487A1 (en) | 2019-06-05 | 2022-04-13 | Basf Se | Electromagnetic wave transmission reducing material |
| KR102651747B1 (ko) | 2021-11-30 | 2024-03-28 | 한국재료연구원 | 자기열량합금 및 이의 제조방법 |
| KR102589531B1 (ko) | 2022-04-20 | 2023-10-16 | 한국재료연구원 | 자기열량합금 및 이의 제조방법 |
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| US428057A (en) * | 1890-05-13 | Nikola Tesla | Pyromagneto-Electric Generator | |
| NL1018668C2 (nl) * | 2001-07-31 | 2003-02-03 | Stichting Tech Wetenschapp | Materiaal geschikt voor magnetische koeling, werkwijze voor het bereiden ervan en toepassing van het materiaal. |
| BR0318065B1 (pt) | 2003-01-29 | 2014-12-23 | Stichting Tech Wetenschapp | Material que pode ser usado para refrigeração magnética, e, método para a fabricação e aplicação do mesmo |
| GB0519843D0 (en) * | 2005-09-29 | 2005-11-09 | Univ Cambridge Tech | Magnetocaloric refrigerant |
| EP2277180B1 (de) * | 2008-04-28 | 2017-08-09 | Technology Foundation - STW | Verfahren zur herstellung von metallbasierten materialien für die magnetische kühlung oder wärmepumpen |
| NZ588752A (en) | 2008-04-28 | 2012-03-30 | Basf Se | Thermomagnetic generator |
| TW201003024A (en) * | 2008-04-28 | 2010-01-16 | Basf Se | Open-cell porous shaped bodies for heat exchangers |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105612593A (zh) * | 2013-08-09 | 2016-05-25 | 巴斯夫欧洲公司 | 含b的磁热材料 |
| CN105684106A (zh) * | 2013-08-09 | 2016-06-15 | 巴斯夫欧洲公司 | 含b的磁热材料 |
| CN105684106B (zh) * | 2013-08-09 | 2018-05-01 | 巴斯夫欧洲公司 | 含b的磁热材料 |
| CN105612593B (zh) * | 2013-08-09 | 2018-06-29 | 巴斯夫欧洲公司 | 含b的磁热材料 |
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| EP2523927A4 (en) | 2016-02-17 |
| US20110167837A1 (en) | 2011-07-14 |
| KR20120135233A (ko) | 2012-12-12 |
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| EP2523927A1 (en) | 2012-11-21 |
| JP2013516780A (ja) | 2013-05-13 |
| BR112012016996A2 (pt) | 2016-04-19 |
| EP2523927B1 (en) | 2016-11-16 |
| TW201145319A (en) | 2011-12-16 |
| WO2011083446A1 (en) | 2011-07-14 |
| US9238592B2 (en) | 2016-01-19 |
| RU2012134280A (ru) | 2014-02-20 |
| CA2786846A1 (en) | 2011-07-14 |
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