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1.
J Chem Phys ; 144(19): 194503, 2016 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-27208954

RESUMO

The temperature-dependent viscosity η(T) is measured for the equilibrium liquid of the chalcogenide Ag-In-Sb-Te (AIST), the first time this has been reported for a material of actual interest for phase-change memory. The measurements, in the range 829-1254 K, are made using an oscillating-crucible viscometer, and show a liquid with high fragility and low viscosity, similar to liquid pure metals. Combining the high-temperature viscosity measurements with values inferred from crystal growth rates in the supercooled liquid allows the form of η(T) to be estimated over the entire temperature range from above the melting point down to the glass transition. It is then clear that η(T) for liquid AIST cannot be described with a single fragility value, unlike other phase-change chalcogenides such as liquid Ge-Sb-Te. There is clear evidence for a fragile-to-strong crossover on cooling liquid AIST, similar to that analyzed in Te85Ge15. The change in fragility associated with the crossover in both these cases is rather weak, giving a broad temperature range over which η(T) is near-Arrhenius. We discuss how such behavior may be beneficial for the performance of phase-change memory. Consideration of the fragile-to-strong crossover in liquid chalcogenides may be important in tuning compositions to optimize the device performance.

2.
Diabetes Obes Metab ; 17(5): 516-9, 2015 May.
Artigo em Inglês | MEDLINE | ID: mdl-25586670

RESUMO

The aim of the present study was to determine whether single-voxel proton magnetic resonance spectroscopy ((1)H-MRS) can non-invasively assess triglyceride content in both supraclavicular fat depots and subcutaneous white adipose tissue (WAT) to determine whether these measurements correlate to metabolic variables. A total of 25 healthy volunteers were studied using (18)F-fluorodeoxyglucose positron emission tomography (PET) and (15)O-H2O PET perfusion during cold exposure, and (1)H-MRS at ambient temperature. Image-guided biopsies were collected from nine volunteers. The supraclavicular triglyceride content determined by (1)H-MRS varied between 60 and 91% [mean ± standard deviation (s.d.) 77 ± 10%]. It correlated positively with body mass index, waist circumference, subcutaneous and visceral fat masses and 8-year diabetes risk based on the Framingham risk score and inversely with HDL cholesterol and insulin sensitivity (M-value; euglycaemic-hyperinsulinaemic clamp). Subcutaneous WAT had a significantly higher triglyceride content, 76-95% (mean ± s.d. 87 ± 5%; p = 0.0002). In conclusion, the triglyceride content in supraclavicular fat deposits measured by (1)H-MRS may be an independent marker of whole-body insulin sensitivity, independent of brown adipose tissue metabolic activation.


Assuntos
Tecido Adiposo Marrom/química , Resistência à Insulina/fisiologia , Insulina/metabolismo , Obesidade/metabolismo , Triglicerídeos/análise , Gordura Abdominal/metabolismo , Tecido Adiposo Branco/química , Adulto , Fatores Etários , Índice de Massa Corporal , HDL-Colesterol , Fluordesoxiglucose F18 , Humanos , Biópsia Guiada por Imagem , Tomografia por Emissão de Pósitrons/métodos , Espectroscopia de Prótons por Ressonância Magnética , Compostos Radiofarmacêuticos/análise , Risco , Temperatura , Circunferência da Cintura
3.
J Chem Phys ; 140(21): 214504, 2014 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-24908023

RESUMO

Published values of crystal growth rates are compared for supercooled glass-forming liquids undergoing congruent freezing at a planar crystal-liquid interface. For the purposes of comparison pure metals are considered to be glass-forming systems, using data from molecular-dynamics simulations. For each system, the growth rate has a maximum value U(max) at a temperature T(max) that lies between the glass-transition temperature T(g) and the melting temperature T(m). A classification is suggested, based on the lability (specifically, the propensity for fast crystallization), of the liquid. High-lability systems show "fast" growth characterized by a high U(max), a low T(max)/T(m), and a very broad peak in U vs. T/T(m). In contrast, systems showing "slow" growth have a low U(max), a high T(max)/T(m), and a sharp peak in U vs. T/T(m). Despite the difference of more than 11 orders of magnitude in U(max) seen in pure metals and in silica, the range of glass-forming systems surveyed fit into a common pattern in which the lability increases with lower reduced glass-transition temperature (T(g)/T(m)) and higher fragility of the liquid. A single parameter, a linear combination of T(g)/T(m) and fragility, can show a good correlation with U(max). For all the systems, growth at U(max) is coupled to the atomic/molecular mobility in the liquid. It is found that, across the diversity of glass-forming systems, T(max)/T(g) = 1.48 ± 0.15.


Assuntos
Cristalização , Vidro/química , Cristais Líquidos/química , Prata/química , Difusão , Cinética , Simulação de Dinâmica Molecular , Viscosidade
4.
Nat Mater ; 11(4): 279-83, 2012 Mar 18.
Artigo em Inglês | MEDLINE | ID: mdl-22426461

RESUMO

Differential scanning calorimetry (DSC) is widely used to study the stability of amorphous solids, characterizing the kinetics of crystallization close to the glass-transition temperature T(g). We apply ultrafast DSC to the phase-change material Ge(2)Sb(2)Te(5) (GST) and show that if the range of heating rates is extended to more than 10(4) K s(-1), the analysis can cover a wider temperature range, up to the point where the crystal growth rate approaches its maximum. The growth rates that can be characterized are some four orders of magnitude higher than in conventional DSC, reaching values relevant for the application of GST as a data-storage medium. The kinetic coefficient for crystal growth has a strongly non-Arrhenius temperature dependence, revealing that supercooled liquid GST has a high fragility. Near T(g) there is evidence for decoupling of the crystal-growth kinetics from viscous flow, matching the behaviour for a fragile liquid suggested by studies on oxide and organic systems.

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