Phonon mechanism for the negative thermal expansion of zirconium tungstate, ZrW<sub>2</sub>O<sub>8</sub>

Rimmer, Leila H. N.; Refson, Keith; Dove, Martin T.

doi:10.1039/d3cp01606d

Cited by 5 publications

(3 citation statements)

References 69 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The interest in these two materials is due to the isotropic nature of the NTE and because they exhibit NTE over a larger temperature range than most materials 9 . ZrW 2 O 8 and HfW 2 O 8 studies are motivated by their application in the engineered thermal expansion of composite materials 10 and recent studies 11–14 have focused on the mechanism leading to NTE. An improved understanding of the fundamental NTE mechanism could be applied to the control of thermal expansion properties of other systems.…”

Section: Introductionmentioning

confidence: 99%

“…Since then, numerous studies have worked to determine the mechanism leading to this uncommon thermal expansion 1 . Many different types of characterization experiments and computational lattice dynamics studies have been performed, including dilatometry, 7,8,23 X‐ray diffraction (XRD), 13,21 neutron diffraction, 7,24,25 X‐ray pair distribution function (PDF) analysis, 12,13 neutron PDF analysis, 11 Raman spectroscopy, 7,26 X‐ray absorption fine structure (XAFS), 27,28 extended XAFS (EXAFS), 12 inelastic neutron scattering (measuring phonon and Grüneisen parameters), 25,29 heat capacity, 21,30 infrared spectroscopy, 31 density functional theory calculations, 13,14,32 and other studies as summarized here 1,33 . It is important to note the following three features concerning the previous studies.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Isotropic negative thermal expansion in ZrW₂O₈ and HfW₂O₈ from 1100 to 1275°C

Hulbert,

Blake,

Mattei

et al. 2024

J Am Ceram Soc.

View full text Add to dashboard Cite

ZrW2O8 (ZrO2•2WO3) and HfW2O8 (HfO2•2WO3) have been the focus of thermal expansion studies due to their isotropic negative thermal expansion (NTE) measured previously at temperatures below 775°C. This work presents measurements of these materials at their thermodynamically stable temperature ranges of 1105 and 1257°C for ZrW2O8 and 1105–1276°C for HfW2O8, where they were characterized with in situ, powder X‐ray diffraction. The linear coefficients of thermal expansion were measured to be −5.52 × 10−6 and −4.87 × 10−6°C−1 for ZrW2O8 and HfW2O8, respectively. The mechanism leading to this NTE is discussed. Powder samples were synthesized by a solution‐based process called the organic–inorganic steric entrapment method. In situ characterization in air was carried out at the National Synchrotron Light Source II using a hexapole lamp, optical furnace and the Advanced Photon Source using a quadrupole lamp, optical furnace to achieve elevated temperatures.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Isotropic negative thermal expansion in ZrW₂O₈ and HfW₂O₈ from 1100 to 1275°C

Hulbert,

Blake,

Mattei

et al. 2024

J Am Ceram Soc.

View full text Add to dashboard Cite

show abstract

“…For some open-framework structure NTE materials, Dove et al proposed the mechanism of rigid unit modes, which is often used to explain the origin of NTE in materials such as ZrW 2 O 8 , Zn(CN) 2 , and AST zeolite . Interestingly, nonrigid NTE modes have been found, for example, in hexagonal symmetry Ln(Co, Fe)(CN) 6 (Ln = La, Pr, Sm, Ho, Lu, Y) systems .…”

Section: Introductionmentioning

confidence: 99%

Critical Role of Nonrigid Unit and Spiral Acoustical Modes in Designing Colossal Negative Thermal Expansion

Gao,

Jiao,

Sprenger

et al. 2024

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Exploring the relationship between thermal expansion and structural complexity is a challenging topic in the study of modern materials where volume stability is required. This work reports a new family of negative thermal expansion (NTE) materials, AM(CN) 4 with A = Li and Na and M = B, Al, Ga, and In. Here, the compounds of LiB(CN) 4 and NaB(CN) 4 were only synthesized; others were purely computationally studied. A critical role of nonrigid vibrational modes and spiral acoustical modes has been identified in NaB(CN) 4 . This understanding has been exploited to design the colossal NTE materials of NaM(CN) 4 (M = Al, Ga, In). A joint study involving synchrotron X-ray diffraction, Raman spectroscopy, and first-principles calculations has been conducted to investigate the thermal expansion mechanism. It has been found that the A atoms can either increase the symmetry of the crystal structure, inducing stronger NTE, or lower the crystal symmetry, thus resulting in positive thermal expansion. Conversely, the M-site atoms do not affect the crystal structure. However, as the radius of the M atoms increases, the ionic nature of the C−M bonds strengthens and the CN vibrations become more flexible, thereby enhancing the NTE behavior. This study provides new insights to aid in the discovery and design of novel NTE materials and the control of thermal expansion.

show abstract

Strong red upconversion luminescence of Yb3+/Er3+ co-doped Sc6WO12 phosphor for optical thermometry

Hu,

Li,

et al. 2025

Journal of Molecular Structure

View full text Add to dashboard Cite

Phonon mechanism for the negative thermal expansion of zirconium tungstate, ZrW₂O₈

Abstract: Negative thermal expansion in ZrW2O8 was investigated using a flexibility analysis of ab-initio phonons. It was shown that no previously proposed mechanism adequately describes the atomic-scale origin of negative thermal...

Cited by 5 publications

References 69 publications

Isotropic negative thermal expansion in ZrW₂O₈ and HfW₂O₈ from 1100 to 1275°C

Isotropic negative thermal expansion in ZrW₂O₈ and HfW₂O₈ from 1100 to 1275°C

Critical Role of Nonrigid Unit and Spiral Acoustical Modes in Designing Colossal Negative Thermal Expansion

Strong red upconversion luminescence of Yb3+/Er3+ co-doped Sc6WO12 phosphor for optical thermometry

Contact Info

Product

Resources

About

Phonon mechanism for the negative thermal expansion of zirconium tungstate, ZrW2O8

Abstract: Negative thermal expansion in ZrW2O8 was investigated using a flexibility analysis of ab-initio phonons. It was shown that no previously proposed mechanism adequately describes the atomic-scale origin of negative thermal...

Cited by 5 publications

References 69 publications

Isotropic negative thermal expansion in ZrW2O8 and HfW2O8 from 1100 to 1275°C

Isotropic negative thermal expansion in ZrW2O8 and HfW2O8 from 1100 to 1275°C

Critical Role of Nonrigid Unit and Spiral Acoustical Modes in Designing Colossal Negative Thermal Expansion

Strong red upconversion luminescence of Yb3+/Er3+ co-doped Sc6WO12 phosphor for optical thermometry

Contact Info

Product

Resources

About

Phonon mechanism for the negative thermal expansion of zirconium tungstate, ZrW₂O₈

Isotropic negative thermal expansion in ZrW₂O₈ and HfW₂O₈ from 1100 to 1275°C

Isotropic negative thermal expansion in ZrW₂O₈ and HfW₂O₈ from 1100 to 1275°C