Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, United States.
J Am Chem Soc. 2011 Feb 16;133(6):1824-31. doi: 10.1021/ja107090n. Epub 2011 Jan 19.
The magnetic field-driven orientation of microcrystals of six diamagnetic layered transition metal oxides (HLaNb(2)O(7), HCa(2)Nb(3)O(10)·0.5H(2)O, KNaCa(2)Nb(4)O(13), KTiTaO(5), KTiNbO(5), and H(2.2)K(1.8)Nb(6)O(17)·nH(2)O) suspended in epoxy resins was studied by X-ray diffraction using permanent magnets producing a 0.8 T field. Although the degree of orientation, quantified as the Hermans order parameter, was strongly affected by the particle size distribution, in all cases microcrystals with ∼1-2 μm lateral dimensions were found to orient with the magnetic field vector in the layer plane. Control of the orientation of ionically conducting layered oxides is of interest for practical applications in batteries and fuel cells. The consistent direction of orientation of the lamellar oxides studied can be rationalized in the framework of a quantitative bond anisotropy model developed by Uyeda (Phys. Chem. Miner.1993, 20, 77-80). The asymmetry of metal-oxygen bonding at the faces of the octahedral layers results in long and short M-O bonds perpendicular to the plane of the sheets. This distortion of the M-O octahedra, which is a structural feature of almost all layered materials that contain octahedral bonding frameworks, gives rise to the diamagnetic anisotropy and results in an easy axis or plane of magnetization in the plane of the sheets.
在环氧树脂中悬浮的六种反铁磁层状过渡金属氧化物(HLaNb(2)O(7)、HCa(2)Nb(3)O(10)·0.5H(2)O、KNaCa(2)Nb(4)O(13)、KTiTaO(5)、KTiNbO(5)和 H(2.2)K(1.8)Nb(6)O(17)·nH(2)O)的微晶在外磁场(由永磁体产生的 0.8 T 磁场)作用下的取向通过 X 射线衍射进行了研究。尽管取向度(用 Hermans 有序参数定量表示)强烈受到颗粒尺寸分布的影响,但在所有情况下,都发现具有约 1-2 μm 横向尺寸的微晶在层平面中沿磁场矢量取向。对于在电池和燃料电池中的实际应用,控制离子导电层状氧化物的取向具有重要意义。Uyeda 提出的定量键各向异性模型(Phys. Chem. Miner.1993, 20, 77-80)可以合理地解释我们所研究的层状氧化物的一致取向方向。八面体层表面处金属-氧键的不对称性导致垂直于薄片平面的长和短 M-O 键。这种 M-O 八面体的变形是几乎所有包含八面体键合框架的层状材料的结构特征,导致反铁磁各向异性,并导致薄片平面中的易磁化轴或平面。