Nejvíce citovaný článek - PubMed ID 31272163
Vitrification and increase of basicity in between ice Ih crystals in rapidly frozen dilute NaCl aqueous solutions
In this work, we focus on the low-temperature behavior of concentrated aqueous solutions of cesium chloride and discover two hydrates of CsCl. We employ four different methods, namely, (i) simple cooling at rates between 0.5 and 80 K s-1, (ii) simple cooling followed by pressurization, (iii) hyperquenching at 106 to 107 K s-1, and (iv) hyperquenching followed by pressurization. Depending on the method, different types of phase behaviors are observed, which encompass crystallization involving freeze-concentration, pressure-induced amorphization, full vitrification, and polyamorphic transformation. The CsCl hydrates discovered in our work cold-crystallize above 150 K upon heating after ultrafast vitrification (routes iii and iv) and show melting temperatures below the eutectic temperature of 251 K. We determine the composition of these hydrates to be CsCl·5H2O and CsCl·6H2O and find evidence for their existence in ESEM, calorimetry, and X-ray diffraction. The dominant and less metastable hydrate is the hexahydrate, where the pentahydrate appears as a minority species. We also reveal the birthplace for the CsCl hydrates, namely, the freeze-concentrated solution (FCS) formed upon cold-crystallization of the fully glassy solution (from iii and iv). The spongy FCS produced upon cooling of the liquid (from i and ii) is incapable of crystallizing CsCl-hydrates. By contrast, the FCS produced upon heating the glassy solution (from iii and iv) shows tiny, fine features that are capable of crystallizing CsCl-hydrates. Our findings contradict the current knowledge that alkali chlorides only have hydrates for the smaller cations Li+ and Na+, but not for the larger cations K+, Rb+, and Cs+ and pave the way for future determination of CsCl-hydrate crystal structures. The pathway to metastable crystalline materials outlined here might be more generally applicable and found in nature, e.g., in comets or on interstellar dust grains, when glassy aqueous solutions crystallize upon heating.
- Publikační typ
- časopisecké články MeSH
This paper deals with CFD analyses of the difference in the nature of the shock waves in supersonic flow under atmospheric pressure and pressure conditions at the boundary of continuum mechanics for electron microscopy. The first part describes the verification of the CFD analyses in combination with the experimental chamber results and the initial analyses using optical methods at low pressures on the boundary of continuum mechanics that were performed. The second part describes the analyses on an underexpanded nozzle performed to analyze the characteristics of normal shock waves in a pressure range from atmospheric pressure to pressures at the boundary of continuum mechanics. The results obtained by CFD modeling are prepared as a basis for the design of the planned experimental sensing of density gradients using optical methods, and for validation, the expected pressure and temperature courses from selected locations suitable for the placement of temperature and pressure sensors are prepared from the CFD analyses.
- Klíčová slova
- Ansys Fluent, CFD, ESEM, Schlieren method, critical flow, nozzle, shock wave,
- Publikační typ
- časopisecké články MeSH
The paper presents a methodology that combines experimental measurements and mathematical-physics analyses to investigate the flow behavior in a nozzle-equipped aperture associated with the solution of its impact on electron beam dispersion in an environmental scanning electron microscope (ESEM). The shape of the nozzle significantly influences the character of the supersonic flow beyond the aperture, especially the shape and type of shock waves, which are highly dense compared to the surrounding gas. These significantly affect the electron scattering, which influences the resulting image. This paper analyzes the effect of aperture and nozzle shaping under specific low-pressure conditions and its impact on the electron dispersion of the primary electron beam.
- Klíčová slova
- Ansys Fluent, CFD, ESEM, critical flow, electron dispersion, nozzle, shock wave,
- Publikační typ
- časopisecké články MeSH
This paper describes the methodology of combining experimental measurements with mathematical-physics analyses in the investigation of flow in the aperture and nozzle. The aperture and nozzle separate the differentially pumped chamber from the specimen chamber in an environmental scanning electron microscope (ESEM). Experimental measurements are provided by temperature and pressure sensors that meet the demanding conditions of cryogenic temperature zones and low pressures. This aperture maintains the required pressure difference between the chambers. Since it separates the large pressure gradient, critical flow occurs on it and supersonic gas flow with the characteristic properties of critical flow in the state variables occurs behind it. As a primary electron beam passes through the differential pumped chamber and the given aperture, the aperture is equipped with a nozzle. The shape of the nozzle strongly influences the character of the supersonic flow. The course of state variables is also strongly influenced by this shape; thus, it affects the number of collisions the primary beam's electrons have with gas molecules, and so the resulting image. This paper describes experimental measurements made using sensors under laboratory conditions in a specially created experimental chamber. Then, validation using mathematical-physical analysis in the Ansys Fluent system is described.
- Klíčová slova
- Ansys Fluent, CFD, ESEM, critical flow, nozzle, numerical simulation,
- Publikační typ
- časopisecké články MeSH