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Title: Studies of high temperature ternary phases in mixed-metal-rich early transition metal sulfide and phosphide systems

Abstract

Investigations of ternary mixed early transition metal-rich sulfide and phosphide systems resulted in the discovery of new structures and new phases. A new series of Zr and Hf - group V transition metal - sulfur K-phases was synthesized and crystallographically characterized. When the group V transition metal was Nb or Ta, the unit cell volume was larger than any previously reported K-phase. The presence of adventitious oxygen was determined in two K-phases through a combination of neutron scattering and X-ray diffraction experiments. A compound Hf 10Ta 3S 3 was found to crystallize in a new-structure type similar to the known gamma brasses. This structure is unique in that it is the only reported "stuffed" gamma-brass type structure. The metal components, Hf and Ta, are larger in size and more electropositive than the metals found in normal gamma brasses (e.g. Cu and Zn) and because of the larger metallic radii, sulfur can be incorporated into the structure where it plays an integral role in stabilizing this phase relative to others. X-ray single-crystal, X-ray powder and neutron powder refinements were performed on this structure. A new structure was found in the ternary Nb-Zr-P system which has characteristics in common with many knownmore » early transition metal-rich sulfides, selenides, and phosphides. This structure has the simplest known interconnection of the basic building blocks known for this structural class. Anomalous scattering was a powerful tool for differentiating between Zr and Nb when using Mo Kα X-radiation. The compounds ZrNbP and HfNbP formed in the space group Prima with the simple Co 2Si structure which is among the most common structures found for crystalline solid materials. Solid solution compounds in the Ta-Nb-P, Ta-Zr-P, Nb-Zr-P, Hf-Nb-P, and Hf-Zr-S systems were crystallographically characterized. The structural information corroborated ideas about bonding in metal-rich compounds.« less

Authors:
 [1]
  1. Iowa State Univ., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Lab., IA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
10119308
Report Number(s):
IS-T-1646
ON: DE94006034; TRN: 94:001654
DOE Contract Number:  
W-7405-ENG-82
Resource Type:
Thesis/Dissertation
Resource Relation:
Other Information: TH: Thesis (Ph.D.); PBD: 4 Jan 1994
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; TRANSITION ELEMENT COMPOUNDS; PHASE STUDIES; CRYSTALLOGRAPHY; SULFIDES; PHOSPHIDES; ZIRCONIUM COMPOUNDS; HAFNIUM COMPOUNDS; NIOBIUM COMPOUNDS; TANTALUM COMPOUNDS; STRUCTURAL CHEMICAL ANALYSIS; CRYSTAL STRUCTURE; 360202; STRUCTURE AND PHASE STUDIES

Citation Formats

Marking, Gregory Allen. Studies of high temperature ternary phases in mixed-metal-rich early transition metal sulfide and phosphide systems. United States: N. p., 1994. Web. doi:10.2172/10119308.
Marking, Gregory Allen. Studies of high temperature ternary phases in mixed-metal-rich early transition metal sulfide and phosphide systems. United States. doi:10.2172/10119308.
Marking, Gregory Allen. Tue . "Studies of high temperature ternary phases in mixed-metal-rich early transition metal sulfide and phosphide systems". United States. doi:10.2172/10119308. https://www.osti.gov/servlets/purl/10119308.
@article{osti_10119308,
title = {Studies of high temperature ternary phases in mixed-metal-rich early transition metal sulfide and phosphide systems},
author = {Marking, Gregory Allen},
abstractNote = {Investigations of ternary mixed early transition metal-rich sulfide and phosphide systems resulted in the discovery of new structures and new phases. A new series of Zr and Hf - group V transition metal - sulfur K-phases was synthesized and crystallographically characterized. When the group V transition metal was Nb or Ta, the unit cell volume was larger than any previously reported K-phase. The presence of adventitious oxygen was determined in two K-phases through a combination of neutron scattering and X-ray diffraction experiments. A compound Hf10Ta3S3 was found to crystallize in a new-structure type similar to the known gamma brasses. This structure is unique in that it is the only reported "stuffed" gamma-brass type structure. The metal components, Hf and Ta, are larger in size and more electropositive than the metals found in normal gamma brasses (e.g. Cu and Zn) and because of the larger metallic radii, sulfur can be incorporated into the structure where it plays an integral role in stabilizing this phase relative to others. X-ray single-crystal, X-ray powder and neutron powder refinements were performed on this structure. A new structure was found in the ternary Nb-Zr-P system which has characteristics in common with many known early transition metal-rich sulfides, selenides, and phosphides. This structure has the simplest known interconnection of the basic building blocks known for this structural class. Anomalous scattering was a powerful tool for differentiating between Zr and Nb when using Mo Kα X-radiation. The compounds ZrNbP and HfNbP formed in the space group Prima with the simple Co2Si structure which is among the most common structures found for crystalline solid materials. Solid solution compounds in the Ta-Nb-P, Ta-Zr-P, Nb-Zr-P, Hf-Nb-P, and Hf-Zr-S systems were crystallographically characterized. The structural information corroborated ideas about bonding in metal-rich compounds.},
doi = {10.2172/10119308},
journal = {},
number = ,
volume = ,
place = {United States},
year = {1994},
month = {1}
}

Thesis/Dissertation:
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