Amorphous sulfur was prepared by rapid compression of liquid sulfur at temperatures above the λ-transition for to preserve the high-temperature liquid structure. We conducted synchrotron high-energy X-ray diffraction and Raman spectroscopy to diagnose the structural evolution of amorphous sulfur from room temperature to post-λ-transition temperature. Discontinuous changes of the first and second peaks in atomic pair-distribution-function, g(r), were observed during the transition from amorphous to liquid sulfur. The average first-neighbor coordination numbers showed an abrupt drop from 1.92 to 1.81. The evolution of the chain length clearly shows that the transition was accompanied by polymeric chains breaking. Furthermore, a re-entry of the λ-transition structure was involved in the heating process. The amorphous sulfur, which inherits the post-λ-transition structure from its parent melts, transformed to the pre-λ-transition liquid structure at around 391 K. Upon further heating, the pre-λ-transition liquid transformed to a post-λ-transition structure through the well-known λ-transition process. This discovery offers a new perspective on amorphous sulfur’s structural inheritance from its parent liquid and has implications for understanding the structure, evolution and properties of amorphous sulfur and its liquids.
Amorphous sulfur (a-S) is prepared by rapidly compressing molten sulfur to high pressure. From differential scanning calorimeter measurements, a large exothermic peak has been observed around 396 K. Online wide-angled x-ray scattering spectra indicate that no crystallization occurs in the temperature range 295-453 K, suggesting that the exothermal process corresponds to an amorphous-to-amorphous transition. The transition from amorphous sulfur to liquid sulfur is further verified by the direct observation of sulfur melt at the temperature of the associated transition. This is the first time of reporting that a-S transforms to liquid sulfur directly, which has avoided a crystallization process. What is more, the transition is an exothermic and a volume expansion process.
A hallmark of nanoscience is size-dependent and distance-dependent physical properties. Although most previous studies focused on optical properties, which are often tuned at nanometer scale, we herein report on the interaction between halide-capped gold nanoparticles (AuNPs) and phosphocholine (PC) liposomes at the sub-Angstrom level. Halide-capped AuNPs are adsorbed by PC liposomes attributable to van der Waals force. Iodide-capped AuNPs interact much more weakly with the liposomes compared with bromide- and chloride-capped AuNPs, as indicated by a liposome leakage assay and differential scanning calorimetry. This is explained by the slightly larger size of iodide separating the AuNP core more from the liposome surface. Cryo-transmission electron microscopy indicates that the liposomes remain intact when mixed with these halide-capped AuNPs of 13 or 70 nm in diameter. Other even larger ligands, including small thiol compounds, DNA oligonucleotides, proteins, and polymers, fully blocked the interaction, whereas AuNPs dispersed in noninteracting ions, including fluoride, phosphate, perchlorate, nitrate, sulfate, and bicarbonate, are still adsorbed strongly by 1,2-dioleoyl- sn-glycero-3-phosphocholine liposomes. Taken together, halides can be used to control interparticle distances at an extremely small scale with remarkable effects on materials properties, allowing surface probing, biosensor development, and fundamental surface science studies.
Addition of β-form nucleating agent (β-NA) to isotactic polypropylene (iPP) can greatly induce the variation of the crystallization of matrix. Here, we introduce high pressure to the crystallization process of β-NA nucleated iPP. It is observed that there is a competition between the effect of high pressure and the nucleation effect of β-NA on crystallization of iPP. With the increasing of high pressure, both the contents of β-iPP and α-iPP decrease while the content of γ-iPP increases. A novel crystalline morphology of γ-iPP with the fragmentations of γ-spherulites regularly organized in a local region is observed. Namely, γ-spherulites grow on the lateral of β-NA needlelike structure. The dual nucleation effects of the special needlelike structure of β-NA towards β/α-iPP and the effect of high pressure which prevents the growth of β-iPP but promotes the growth of γ-iPP are the main mechanisms for the novel crystalline morphology of γ-iPP. Specifically, the mixed polymorphic β/γ-iPP can be achieved under a certain pressure. This possibly enlarges the application of iPP material.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.