Self-assembly of a triply periodic continuous mesophase with Fddd symmetry in simple one-component liquids

Agosta, Lorenzo; Metere, Alfredo; Oleynikov, Peter; Dzugutov, Mikhail

doi:10.1063/5.0006096

Cited by 5 publications

(4 citation statements)

References 25 publications

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“…In a recent theoretical investigation, it was shown that such Fddd mesophases could be stabilized even in single-component systems, in which case, the diffusivity of constituent particles was practically identical to that of the liquid phase. 75 These Fddd mesophases were shown to be stable at specific volume ratios between the different block copolymers or equivalently at a specific density for the single-component systems, 75 which by analogy lends weight to our hypothesis that steric considerations are the key parameter in the stability of γ-Na 3 PS 4 .…”

Section: ■ Resultsmentioning

confidence: 81%

Insights into the Rich Polymorphism of the Na⁺ Ion Conductor Na₃PS₄ from the Perspective of Variable-Temperature Diffraction and Spectroscopy

et al. 2021

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Solid electrolytes are crucial for next-generation solid-state batteries, and Na 3 PS 4 is one of the most promising Na + conductors for such applications, despite outstanding questions regarding its structural polymorphs. In this contribution, we present a detailed investigation of the evolution in structure and dynamics of Na 3 PS 4 over a wide temperature range 30 < T < 600 °C through combined experimental−computational analysis. Although Bragg diffraction experiments indicate a second-order phase transition from the tetragonal ground state (α, P4̅ 2 1 c) to the cubic polymorph (β, I4̅ 3m) above ∼250 °C, pair distribution function analysis in real space and Raman spectroscopy indicate remnants of a tetragonal character in the range 250 < T < 500 °C, which we attribute to dynamic local tetragonal distortions. The first-order phase transition to the mesophasic high-temperature polymorph (γ, Fddd) is associated with a sharp volume increase and the onset of liquid-like dynamics for sodium-cations (translational) and thiophosphate-polyanions (rotational) evident by inelastic neutron and Raman spectroscopies, as well as pair-distribution function and molecular dynamics analyses. These results shed light on the rich polymorphism of Na 3 PS 4 and are relevant for a range host of high-performance materials deriving from the Na 3 PS 4 structural archetype.

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Section: ■ Resultsmentioning

confidence: 81%

Insights into the Rich Polymorphism of the Na⁺ Ion Conductor Na₃PS₄ from the Perspective of Variable-Temperature Diffraction and Spectroscopy

et al. 2021

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“…These systems are mesophasic, with properties in between solid and liquid, and exhibit remarkable mobility of their constituent atoms. In a recent theoretical investigation it was shown that such mesophases could be stabilized even in single-component systems in which case the diffusivity of constituent particles was practically identical to that of the liquid phase 77 . These mesophases were shown to be stable at specific volume ratios between the different block copolymers or, equivalently at a specific density for the single-component systems 77 ; which by analogy lends weight to our hypothesis that steric considerations are the key parameter in the stability of γ-Na3PS4.…”

Section: Figure 9: Diffraction Analysis Of γ-Na3ps4 (A) Bragg Diffractogram At 550 °C Indexed In the Fddd Space Group And (B) Comparison mentioning

confidence: 99%

Insights into the rich polymorphism of the Na+ ion conductor Na3PS4 from the perspective of variable-temperature diffraction and spectroscopy

Famprikis

Bouyanfif²,

Canepa³

et al. 2021

Preprint

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Solid electrolytes are crucial for next generation solid state batteries and Na3PS4 is one of the most promising Na+ conductors for such applications. In this contribution, we present a detailed investigation of the evolution in structure and dynamics of Na3PS4 under the effect of temperature in the range 30 < T < 600 °C through combined experimental-computational analysis. Although x ray Bragg diffraction experiments indicate a second order phase transition from the tetragonal ground state (α, P-421c) to the cubic polymorph (β, I-43m), pair distribution function analysis in real space and Raman spectroscopy indicate remnants of tetragonal character in the range 250 < T < 500 °C which we attribute to dynamic local tetragonal distortions. The first order phase transition to the mesophasic high temperature polymorph (γ, Fddd) is associated with a sharp volume increase and the onset of liquid like diffusive dynamics for sodium-cations (translative) and thiophosphate-polyanions (rotational) evident by inelastic neutron- and Raman- spectroscopies, as well as pair-distribution function and molecular dynamics. These results shed light on the rich polymorphism in Na3PS4 and are relevant for a host of high performance materials deriving from the Na3PS4 structural archetype.

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“…Two adjacent zigzag arrays are joined to each other with a torsional angle φ. The relationship between the torsional angle φ and the lattice parameters is described by a / b = tan(φ/2). − The torsional angle of Fddd phase formed by the trans -star copolymer was hence found to be 53°.…”

Section: Resultsmentioning

confidence: 99%

Self-Assembly Behavior of Sugar-Based Block Copolymers in the Complex Phase Window Modulated by Molecular Architecture and Configuration

Chen

et al. 2022

Macromolecules

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Sugar-based block copolymers (BCPs) have emerged as a class of green material capable of self-assembling into ordered structures with sub-10 nm feature size in the oligomeric regime. Here, we reveal the strong effects of molecular architecture and configuration on the self-assembly behavior of the monodisperse maltose (Glc 2 )solanesol (Sol) BCPs bearing linear and A 2 B 2 miktoarm star architectures in the complex phase window. Double gyroid (DG) and hexagonal perforated layer (HPL) with ABC stacking of the perforation were observed with strong architectural effects on their order−order transition (OOT) behavior. The oligomeric nature of the miktoarm star BCP amplified the role of the configuration prescribed by the substituted positions of the block chains at the benzene core. The trans configuration set by the 1,4-substitution of the two Glc 2 blocks at the core exerted a stronger steric hindrance to the formation of hydrogen bonding of Glc moiety than the cis configuration prescribed by the 1,3-substitution. The more effective formation of hydrogen bonding in the cis-star BCP led to a stronger resistance against the bending of the sugar domain interface and hence narrowed down the window of the higher-curvature morphology. The HPL-to-DG transition was intervened by the Fddd phase in the trans-star copolymer, which was attributed to the larger asymmetry in the unit cell dimensions of the hexagonal unit cell of HPL phase.

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Self-assembly of a triply periodic continuous mesophase with Fddd symmetry in simple one-component liquids

Cited by 5 publications

References 25 publications

Insights into the Rich Polymorphism of the Na⁺ Ion Conductor Na₃PS₄ from the Perspective of Variable-Temperature Diffraction and Spectroscopy

Insights into the Rich Polymorphism of the Na⁺ Ion Conductor Na₃PS₄ from the Perspective of Variable-Temperature Diffraction and Spectroscopy

Insights into the rich polymorphism of the Na+ ion conductor Na3PS4 from the perspective of variable-temperature diffraction and spectroscopy

Self-Assembly Behavior of Sugar-Based Block Copolymers in the Complex Phase Window Modulated by Molecular Architecture and Configuration

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Self-assembly of a triply periodic continuous mesophase with Fddd symmetry in simple one-component liquids

Cited by 5 publications

References 25 publications

Insights into the Rich Polymorphism of the Na+ Ion Conductor Na3PS4 from the Perspective of Variable-Temperature Diffraction and Spectroscopy

Insights into the Rich Polymorphism of the Na+ Ion Conductor Na3PS4 from the Perspective of Variable-Temperature Diffraction and Spectroscopy

Insights into the rich polymorphism of the Na+ ion conductor Na3PS4 from the perspective of variable-temperature diffraction and spectroscopy

Self-Assembly Behavior of Sugar-Based Block Copolymers in the Complex Phase Window Modulated by Molecular Architecture and Configuration

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Insights into the Rich Polymorphism of the Na⁺ Ion Conductor Na₃PS₄ from the Perspective of Variable-Temperature Diffraction and Spectroscopy

Insights into the Rich Polymorphism of the Na⁺ Ion Conductor Na₃PS₄ from the Perspective of Variable-Temperature Diffraction and Spectroscopy