Local Structure of Zr(OH)4 and the Effect of Calcination Temperature from X-ray Pair Distribution Function Analysis

King, Graham; Soliz, Jennifer R.; Gordon, Wesley O.

doi:10.1021/acs.inorgchem.7b03137

Title: Local Structure of Zr(OH)₄ and the Effect of Calcination Temperature from X-ray Pair Distribution Function Analysis

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Abstract

Analysis of X-ray pair distribution function data has provided a detailed picture of the local structure of amorphous Zr(OH)₄ and its thermal decomposition into ZrO₂. In the untreated phase, the Zr atoms tend to be coordinated by six or seven oxygen atoms. The Zr centered polyhedra connect to each other primarily by sharing edges, but also with a significant amount of corner sharing, to form two-dimensional sheets in which the Zr are connected to an average of about five other Zr. This local structure is related to the structure of monoclinic ZrO₂ and can be derived from it by removing certain Zr neighbors to form sheets and reduce the corner to edge sharing ratio. The maximum correlation length in Zr(OH)₄ is about 12 Å. Heating up to 125 °C results in significant water loss but does not alter the network of Zr and bridging O atoms. Additional water loss caused by heating to 250 °C triggers a reorganization into a new type of amorphous phase with a three-dimensional network and a greater number of Zr–Zr neighbors. Further heating to 330 °C causes crystallization into a mixture of tetragonal and monoclinic ZrO₂, with the minor tetragonal phase having a smaller averagemore »« less

Authors:

^[1]; Soliz, Jennifer R. ^[2]; Gordon, Wesley O. ^[2]

Independent Research Consultant, Los Alamos, NM (United States)
Edgewood Chemical Biological Center, Aberdeen Proving Ground, MD (United States)

Publication Date:: 2018-02-12

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1424779

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: Inorganic Chemistry

Additional Journal Information:: Journal Volume: 57; Journal Issue: 5; Journal ID: ISSN 0020-1669

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: ENGLISH

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemical structure; oxides; anions; phase transitions; order

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                    King, Graham, Soliz, Jennifer R., and Gordon, Wesley O. Local Structure of Zr(OH)4 and the Effect of Calcination Temperature from X-ray Pair Distribution Function Analysis.  United States: N. p., 2018. 
Web.  doi:10.1021/acs.inorgchem.7b03137.

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                    King, Graham, Soliz, Jennifer R., & Gordon, Wesley O. Local Structure of Zr(OH)4 and the Effect of Calcination Temperature from X-ray Pair Distribution Function Analysis.  United States.  https://doi.org/10.1021/acs.inorgchem.7b03137

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                    King, Graham, Soliz, Jennifer R., and Gordon, Wesley O. Mon .  
"Local Structure of Zr(OH)4 and the Effect of Calcination Temperature from X-ray Pair Distribution Function Analysis".  United States.  https://doi.org/10.1021/acs.inorgchem.7b03137.  https://www.osti.gov/servlets/purl/1424779.

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@article{osti_1424779,

  title        = {Local Structure of Zr(OH)4 and the Effect of Calcination Temperature from X-ray Pair Distribution Function Analysis},

  author       = {King, Graham and Soliz, Jennifer R. and Gordon, Wesley O.},

  abstractNote = {Analysis of X-ray pair distribution function data has provided a detailed picture of the local structure of amorphous Zr(OH)4 and its thermal decomposition into ZrO2. In the untreated phase, the Zr atoms tend to be coordinated by six or seven oxygen atoms. The Zr centered polyhedra connect to each other primarily by sharing edges, but also with a significant amount of corner sharing, to form two-dimensional sheets in which the Zr are connected to an average of about five other Zr. This local structure is related to the structure of monoclinic ZrO2 and can be derived from it by removing certain Zr neighbors to form sheets and reduce the corner to edge sharing ratio. The maximum correlation length in Zr(OH)4 is about 12 Å. Heating up to 125 °C results in significant water loss but does not alter the network of Zr and bridging O atoms. Additional water loss caused by heating to 250 °C triggers a reorganization into a new type of amorphous phase with a three-dimensional network and a greater number of Zr–Zr neighbors. Further heating to 330 °C causes crystallization into a mixture of tetragonal and monoclinic ZrO2, with the minor tetragonal phase having a smaller average domain size. Here, the tetragonal component vanishes by 900 °C.},

  doi          = {10.1021/acs.inorgchem.7b03137},

  journal      = {Inorganic Chemistry},

  number       = 5,

  volume       = 57,

  place        = {United States},

  year         = {2018},

  month        = {2}

}

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Title: Local Structure of Zr(OH)4 and the Effect of Calcination Temperature from X-ray Pair Distribution Function Analysis

Abstract

Citation Formats

Title: Local Structure of Zr(OH)₄ and the Effect of Calcination Temperature from X-ray Pair Distribution Function Analysis