Synthsis, structure and physical property of vanadate garnets

钒酸盐石榴石的合成、结构及物性

• 批准号: 14540449
• 负责人: IISHI Kazuake
• 金额: $ 1.98万
• 依托单位: Yamaguchi University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14540449/
• 关键词: Vanadate garnet; Crystal chemistry; Solid solution; Flux method; Morphplogy; Surface kinetics; 構造解析; イオン半径; モルホロジー; 抵抗加熱型FZ単結晶育成装置; SHG結晶; Li_3VO_4; リートベルト構造解析; ヤーン・テラー効果; HSAB原理

1 Experiments were conducted to synthesize vanadate garnets of the following 5 types ; Type3:{A^+_2A^<2+>}[M^<2+>M^<3+>]-(V_3)O_<12>, Type 4:{A^+A^<2+>_2}[M^+M^<3+>](V_3)O_<12>, Type 5:{A^+A^<2+>_2}[M^<2+>_2](V_3)O_<12>, Type 6:{A^<2+>_3}[M^+M^<2+>](V_3)O_<12> and Type 7:{□_<0.5>A^<2+>_<2.5>}[M^<2+>_2](V_3)O_<12>, where A^+=Li^+,Cu^+,Na^+,Ag^+ and K^+;A^<2+>=Cd^<2+>,Ca^<2+>,Sr^<2+> and Pb^<2+>;M^+=Li^+;M^<2+>=Ni^<2+>,Mg^<2+>,Co^<2+>,Cu^<2+>,Zn^<2+>,Mn^<2+> and Cd^<2+>;M^<3+>=Cr^<3+> and Fe^<3+>. New variations of {Na_2Ca}[NiFe^<3+>](V_3)O_<12>,{A^+Ca_2}[LiCr^<3+>](V_3)O_<12>, where A^+=Li^+ and Na^+,{A^+Ca_2}[LiFe^<3+>](V_3)O_<12>, where A^+=Li^+,Cu^+,Na^+ and Ag^+,{LiCa_2}[M^<2+>_2](V_3)O_<12>, where M^<2+>=Co^<2+> and Mn^<2+>,{KCa_2}[Mn_2](V_3)O_<12>,{Ca_3}[LiCd](V_3)O_<12> and {Pb_3}[LiM^<2+>](V_3)O_<12>, where M^<2+>=Mg^<2+>,Co^<2+>,Zn^<2+>,Mn^<2+> and Cd^<2+> were prepared as phase-pure garnets for the first time. Garnets were formed only a few in both types 3 and 4. In types 5,6 … More and 7, the variety of garnets formed was greatly limited by the replacement of Ca^<2+> by Sr^<2+> as compared with that being not so much limited by the replacement of Ca^<2+> by Pb^<2+>, though the effective ionic radius of Pb^<2+> is larger than that of Sr^<2+>. This is ascribed to "the hard and soft acids and bases principle". In types 5,6 and 7, in the case of M^<2+>=Cu^<2+>, the variety of garnets formed was fairly limited due to the "the Jahn-Teller effect of Cu^<2+>".2 The morphologies of vanadate garnets (NaCa_2M_2V_3O_<12>,M=Ni,Mg or Co) were studied by growing well-formed crystals from sodium vanadate flux. The first rank F-faces were determined by growing crystals at low supersaturation levels and were found to be the {110} face at lower temperature and the {211} face at higher temperature. This change was ascribed to a change in the ratio of the bond lengths at the octahedral site to that of the dodecahedral site with increasing temperature. When crystals grew larger in the lower temperature region, predominantly {211} faces appeared in addition to {110} faces, whereas in the higher temperature region, {110} faces were predominant over {211} faces. The reason for these phenomena was ascribed to the surface kinetics caused by an increase in the rate of mineral nutrient transport to the surface of the crystal with increasing crystal size. Less

1实验合成了以下5种钒酸石榴石；Type3: {^ + _2A ^ < 2 + >} [M ^ < 2 + > M ^ < 3 + >)——(V_3) O_ 12 > <,类型4:{^ + ^ < 2 + > _2}[M ^ + M ^ < 3 + >] (V_3) O_ 12 > <,类型5:{^ + ^ < 2 + > _2}[M ^ < 2 + > _2) O_ (V_3) < 12 >,类型6:{一个^ < 2 + > _3}[M ^ + M ^ 2 < + >] (V_3) O_ < 12 >和类型7:{□一^ _ < 0.5 > < 2 + > _ < 2.5 >}[M ^ < 2 + > _2) O_ (V_3) < 12 >,在李^ + = ^ +铜^ +、Na ^ + Ag)和K ^ ^ + +;Cd ^ ^ < 2 + > = < 2 + >, Ca ^ < 2 + >, Sr ^ < 2 + >和Pb ^ < 2 + >,李米^ + = ^ +;倪M ^ < 2 + > = ^ < 2 + >, Mg ^ < 2 + >,公司^ < 2 + >,铜^ < 2 + >,锌^ < 2 + >,Mn ^ ^ < 2 + >和Cd < 2 + >;M^<3+>=Cr^<3+>和Fe^<3+>。{Na_2Ca}的新变化(镍铁^ < 3 + >](V_3) O_ 12 > <, {^ + Ca_2} [LiCr ^ < 3 + >] (V_3) O_ < 12 >,在李^ + = ^ ^ + +和Na, {^ + Ca_2}[生活^ < 3 + >](V_3) O_ < 12 >,在李^ + = ^ +铜^ +、Na和Ag) ^ ^ + + {LiCa_2} [M ^ < 2 + > _2) O_ (V_3) < 12 >,其中M ^ < 2 + > =公司^ < 2 + >和Mn ^ < 2 + >, {KCa_2} [Mn_2] (V_3) O_ 12 > <, {Ca_3} [LiCd] (V_3) O_ < 12 >和{Pb_3} (LiM ^ < 2 + >] (V_3) O_ < 12 >,其中M ^ < 2 + > = Mg ^ < 2 + >,公司^ < 2 + >,锌^ < 2 + >,Mn ^ ^ < 2 + >和Cd < 2 + >是准备phase-pure装货用的第一次。在第3型和第4型中均形成少量石榴石。在5、6、6、7型石榴石中，Ca^<2+>被Sr^<2+>取代对石榴石种类的限制较大，而Ca^<2+>被Pb^<2+>取代对石榴石种类的限制较小，但Pb^<2+>的有效离子半径大于Sr^<2+>。这被归因于“软硬酸碱原理”。在类型5、6和7中，当M^<2+>=Cu^<2+>时，由于“Cu^<2+>的Jahn-Teller效应”，形成的石榴石种类相当有限用钒酸钠助熔剂生长出结构良好的钒酸石榴石（NaCa_2M_2V_3O_<12 bbb_，M=Ni，Mg或Co）的形貌。通过在低过饱和水平下生长晶体确定了一级f面，发现在较低温度下为{110}面，在较高温度下为{211}面。这种变化是由于八面体位点与十二面体位点的键长之比随着温度的升高而变化。当晶体在低温区变大时，{211}面和{110}面都以{211}面为主，而在高温区，{110}面多于{211}面。产生这些现象的原因是由于晶体尺寸增大，矿物营养物质向晶体表面运输的速率增加而引起的表面动力学。少

项目成果

The crystal structure of synthetic paleuzoanite Ca_2NaMn_2V_3O_<12>

合成古石榴石Ca_2NaMn_2V_3O_<12>的晶体结构

• 发表时间: 2004
• 期刊: Applied Mineralogy(Pecchio, et al.(eds))(CAM-BR, Sao Paulo)
• 作者: Nakatsuka;A.
• 通讯作者: A.

Isomorphous substitutions in vanadate garnets

钒酸盐石榴石中的同晶取代

• 发表时间: 2006
• 期刊: Neues Jahrbuch fur Mineralogie Abhandlung 18(In press)
• 作者: K.Iishi

Single crystal X-ray diffraction study of the vanadate garnet Ca2NaZn2V3O12

• DOI: 10.1016/j.materresbull.2004.03.013
• 发表时间: 2004-06
• 期刊: Materials Research Bulletin
• 影响因子: 5.4
• 作者: A. Nakatsuka;Y. Ikuta;A. Yoshiasa;K. Iishi

Morphology of flux-grown vanadate garnets

助熔剂生长的钒酸盐石榴石的形态

• 发表时间: 2006
• 期刊: Journal of Crystal Growth 290(In press)
• 作者: K.Iishi;K.Iishi
• 通讯作者: K.Iishi

The Crystal structure of synthetic palenzoanite Ca_2NaMn_2V_3O_<12>

合成古绿石Ca_2NaMn_2V_3O_<12>的晶体结构

• 发表时间: 2004
• 期刊: Applied Mineralogy, Pecchio et al. (eds) 2004 ICAM-BR, Sao Paulo
• 作者: Iishi;K.;A.Nakatsuka;A.Nakatsuka
• 通讯作者: A.Nakatsuka