【公開日：2024.07.25】【最終更新日：2024.06.22】
課題データ / Project Data
課題番号 / Project Issue Number
23NU0038
利用課題名 / Title
(V,Cr,Mo)P4 多成分系リン化物の均一性
利用した実施機関 / Support Institute
名古屋大学 / Nagoya Univ.
機関外・機関内の利用 / External or Internal Use
内部利用（ARIM事業参画者以外）/Internal Use (by non ARIM members)
技術領域 / Technology Area
【横断技術領域 / Cross-Technology Area】（主 / Main）計測・分析/Advanced Characterization（副 / Sub）-
【重要技術領域 / Important Technology Area】（主 / Main）マルチマテリアル化技術・次世代高分子マテリアル/Multi-material technologies / Next-generation high-molecular materials（副 / Sub）-
キーワード / Keywords
multicomponent transition metal, phosphide, homogeneity, ,電子顕微鏡/ Electronic microscope,異種材料接着・接合技術/ Dissimilar material adhesion/bonding technology
利用者と利用形態 / User and Support Type
利用者名（課題申請者）/ User Name (Project Applicant)
長谷川 正
所属名 / Affiliation
名古屋大学大学院工学研究科
共同利用者氏名 / Names of Collaborators in Other Institutes Than Hub and Spoke Institutes
チャン チュンチン,佐々木 拓也,丹羽 健
ARIM実施機関支援担当者 / Names of Collaborators in The Hub and Spoke Institutes
樋口公孝,山本悠太,武藤俊介
利用形態 / Support Type
（主 / Main）技術代行/Technology Substitution（副 / Sub）-
利用した主な設備 / Equipment Used in This Project
報告書データ / Report
概要（目的・用途・実施内容）/ Abstract (Aim, Use Applications and Contents)
Homogeneous multicomponent material has gained certain interest in recent material engineering. This differs from conventional material design methodology, in which only minor amount of an element are added to a base material to enhance its property (corner of the phase diagram). The idea of combining equimolar amount of distinct elements into single structure, present a new material design route that explore the center of the phase diagram. Until now, new material properties that cannot be explained by the constituent endmembers was found [1,2]. In the exploration of new homogeneous multicomponent ceramics, we have successfully synthesized a new multicomponent transition metal phosphide (V,Cr,Mo)P4 through high-pressure synthesis technique. Herein, to understand the homogeneity of this material at atomic scale, STEM analysis was carried out in this experiment.
実験 / Experimental
Sample of (V,Cr,Mo)P4 was prepared by using bulk vanadium (Mitsuwa Chemicals Co., Ltd., 99.9%, piece 2-3×5-7×10-30 mm), chromium (Nilaco Co., 99.9%, chunk 1-3 mm), and molybdenum (Kojundo Chemical Lab. Co., Ltd., 99.9%, chip 10x10x1 mm) weighted at 1:1:1 molar ratio. Then, the metals are alloyed using an arc melting process followed by liquid quenching and finally mixed with red phosphorus (Kojundo Chemical Laboratory. Co., Ltd., 99.99 %, powder < 600 μm) inside an Ar-filled glove box with a molar ratio of alloy: phosphorus =1: 6 for 30 minutes. High-pressure syntheses were carried out using a 250-ton DIA-type cubic multi-anvil-large-volume press (LVP). The conditions for the high-pressure syntheses for the V-Cr-Mo-P sample at pressure, P = 4 GPa, temperature, T = 1173 K, and resistance heating time, t = 0.5 hour. A scanning transmission electron microscope (JEM-ARM200/F Cold, accelerating voltage: 200 kV) was used to study the crystal structure as well as the atomic-scale homogeneity of the products.
結果と考察 / Results and Discussion
By
adding distinct elements into the lattice of CrP4,
(V,Cr,Mo)P4
was successfully synthesized.
The
HAADF-STEM image on the [001] projection of the sample is shown in
Figure 1a, accompanied by contrast analysis results presented in
Figure 1b and Figure 1c. Compared to vanadium and chromium,
molybdenum is larger in atomic size and has a higher atomic number
(the atomic radii for V, Cr, and Mo are 1.71 Å, 1.66 Å,
and 1.90 Å, respectively)
[3].
Generally,
larger atoms have difficulties in integrating into the lattice of
smaller atoms, often leading to the formation of a secondary phase or
partial precipitation resulting in clustering and inhomogeneity.
Given the higher atomic number of Mo, its columns should be
distinguishable in the atomic-scale STEM images if there is clear
clustering in the sample.
However,
the intensities of the signals remain constant across all points,
suggesting a homogenous distribution of Mo throughout the structure.
The gradual decrease in intensity observed in the STEM image is
attributed to the varying sample thickness, with the left side being
thicker than the right. Despite the size difference among V, Cr, and
Mo, these transitional metals are uniformly incorporated into the
same structure, as corroborated by the EDS analysis. This all
confirms the sample is a homogeneous CrP4-type
phosphide (V,Cr,Mo)P4.
図・表・数式 / Figures, Tables and Equations
Figure 1 The STEM analysis of a) [001] projection HAADF image of (V,Cr,Mo)P4 and the corresponding contrast profiles of transition metal sites in b) horizontal direction and c) in the vertical direction (the analysis lines are also marked in the HAADF image). The intensity of the contrast profiles represents the position of atoms; a metal-metal distance of 5.26 Å corresponds to the a-axis direction and is consistent with the lattice parameter for (V,Cr,Mo)P4. The crystal structures corresponding to the projected directions are also shown in the images (orange: phosphorus; blue: transition metals).
その他・特記事項（参考文献・謝辞等） / Remarks(References and Acknowledgements)
・References : [1] B.Cantor, I.T.H. Chang, P. Knight, A.J.B. Vincent, Mater. Sci. Eng. A
375–377 (2004) 213–218.
[2] J.-W.
Yeh, S.-K. Chen, S.-J. Lin, J.-Y. Gan, T.-S. Chin, T.-T. Shun, C.-H.
Tsau, S.-Y. Chang, Adv. Eng. Mater., 6 (2004) 299–303.
[3] E.Clementi, D.L. Raimondi, W.P. Reinhardt, J. Chem. Phys., 47 (1967)
1300–1307.
・C.-C. Chang, T. Sasaki, S. Muto, N. Gaida, K. Niwa, M. Hasegawa. In preparation.
成果発表・成果利用 / Publication and Patents
論文・プロシーディング（DOIのあるもの） / DOI (Publication and Proceedings)
口頭発表、ポスター発表および、その他の論文 / Oral Presentations etc.
特許 / Patents
特許出願件数 / Number of Patent Applications：0件
特許登録件数 / Number of Registered Patents：0件