Vapor-deposited amorphous solid water (ASW) is the most abundant solid molecular material in space, where it plays a direct role in both the formation of more complex chemical species and the aggregation of icy materials in the earliest stages of planet formation. Nevertheless, some of its low temperature physics such as the collapse of the micropore network upon heating are still far from being understood. Here we characterize the nature of the micropores and their collapse using neutron scattering of gram-quantities of D2O-ASW of internal surface areas up to 230 ± 10 m(2) g(-1) prepared at 77 K. The model-free interpretation of the small-angle scattering data suggests micropores, which remain stable up to 120-140 K and then experience a sudden collapse. The exact onset temperature to pore collapse depends on the type of flow conditions employed in the preparation of ASW and, thus, the specific surface area of the initial deposit, whereas the onset of crystallization to cubic ice is unaffected by the flow conditions. Analysis of the small-angle neutron scattering signal using the Guinier-Porod model suggests that a sudden transition from three-dimensional cylindrical pores with 15 Å radius of gyration to two-dimensional lamellae is the mechanism underlying the pore collapse. The rather high temperature of about 120-140 K of micropore collapse and the 3D-to-2D type of the transition unraveled in this study have implications for our understanding of the processing and evolution of ices in various astrophysical environments.
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http://dx.doi.org/10.1039/c4cp00593g | DOI Listing |
Nanomaterials (Basel)
December 2024
Emerging Technologies Research Center, XPANCEO, Internet City, Emmay Tower, Dubai, United Arab Emirates.
Due to their high refractive index, record optical anisotropy and a set of excitonic transitions in visible range at a room temperature, transition metal dichalcogenides have gained much attention. Here, we adapted a femtosecond laser ablation for the synthesis of WSe nanoparticles (NPs) with diameters from 5 to 150 nm, which conserve the crystalline structure of the original bulk crystal. This method was chosen due to its inherently substrate-additive-free nature and a high output level.
View Article and Find Full Text PDFJ Phys Chem B
January 2025
Homi Bhabha National Institute, Anushakti Nagar, Mumbai 400094, India.
Introduction of non-DLVO forces by nonionic surfactants brings about fascinating changes in the phase behavior of silica nanosuspensions. We show here that alterations in the interaction and wetting properties of negatively charged silica nanoparticles (Ludox® LS) in the presence of polyethylene oxide-polypropylene oxide-polyethylene oxide-based triblock copolymers called Pluronics lead to the formation of stable o/w Pickering emulsions and interparticle attraction-induced thermoresponsive liquid-liquid phase separations. The results make interesting comparisons with those reported for Ludox® TM nanosuspensions comprising larger silica nanoparticles.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry, Institute for Advanced Materials and Manufacturing, University of Tennessee, Knoxville, Tennessee 37996, United States.
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View Article and Find Full Text PDFNanoscale
January 2025
Department of Biomedical Engineering, Southern University of Science and Technology, Shenzhen 518055, China.
The highly anisotropic and nonadditive nature of nanoparticle surfaces restricts their characterization by limited types of techniques that can reach atomic or molecular resolution. While small-angle neutron scattering (SANS) is a unique tool for analyzing complex systems, it has been traditionally considered a low-resolution method due to its limited scattering vector range and wide wavelength spread. In this article, we present a novel perspective on SANS by showcasing its exceptional capability to provide molecular-level insights into nanoparticle interfaces.
View Article and Find Full Text PDFChem Sci
December 2024
College of Science, Engineering and Environment, University of Newcastle Callaghan NSW 2308 Australia.
The inductive effect is a central concept in chemistry and is often exemplified by the p values of acetic acid derivatives. The reduction in p is canonically attributed to the reduction in the electron density of the carboxylate group through the inductive effect. However, wave functional theory calculations presented herein reveal that the charge density of the carboxylate group is not explained by the inductive effect.
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