Plasmonic-excitonic multi-hybrid glass-based nanocomposites incorporating Ag plus core-shell CdSe/CdS and alloyed CdSxSe1−x nanoparticles

Successful fabrication of glass-based hybrid nanocomposites (GHNCs) incorporating Ag, core-shell CdSe/CdS and CdS_xSe_1?x nanoparticles (NPs) is herein reported. Both metallic (Ag) and semiconductor (CdSe/CdS) NPs were pre-synthesized, suspended in colloids and added into the sol-gel reaction medium which was used to fabricate the GHNCs. During fabrication of the nanocomposites a fraction (20–60%) of core-shell CdSe/CdS NPs was alloyed into CdS_xSe_1?x (0.20 < x < 0.35) NPs without changing morphology. Modulation of in situ alloying is possible via the relative content of organics added into the sol-gel protocol. Within colloids Ag (core-shell CdSe/CdS) NPs presented average diameter and polydispersity index of 49.5 nm (4.2 nm) and 0.41 (0.21), respectively. On the other hand, the Ag (core-shell CdSe/CdS) NPs’ average diameter and polydispersity index assessed from the GHNCs were respectively 51.5 nm (4.1 nm) and 0.43 (0.25), revealing negligible aggregation of the nanophases within the glass template. The new GHNCs herein introduced presented two independent excitonic transitions associated to homogenously dispersed semiconductor NPs, peaking around 420 nm (core-shell CdSe/CdS) and 650 nm (CdS_xSe_1?x) and matching the plasmonic resonance (Ag NPs) in the 400–500 nm range. We envisage that the new GHNCs represent very promising candidates for superior light manipulation while illuminated with multiple laser beams in quantum interference-based devices.     

Temperature cycling and its effect on mechanical behaviours of highporosity chalks

Temperature history can have a significant effect on the strength of water-saturated chalk.In this study,hydrostatic stress cycles are applied to understand the mechanical response of chalk samples exposed to temperature cycling between each stress cycle,compared to the samples tested at a constant temperature.The total accumulated strain during a stress cycle and the irreversible strain are reported.Chalk samples from Kansas(USA)and Mons(Belgium),with different degrees of induration(i.e.amount of contact cementation),were used.The samples were saturated with equilibrated water(polar)and nonpolar Isopar H oil to quantify water weakening.All samples tested during 10 stress cycles with varying temperature(i.e.temperature cycled in between each stress cycle)accumulated more strain than those tested at constant temperatures.All the stress cycles were performed at 30℃.The two chalk types behaved similarly when saturated with Isopar H oil,but differently when saturated with water.When saturated with water,the stronger Kansas chalk accumulated more total strain and more irreversible strain within each stress cycle than the weaker Mons chalk.     

A quarter century of wine pigment discovery

The red grape berry pigments, anthocyanins, were characterized in the early 20th century, but investigations of wine pigments were stymied during that era. The question of their identity was a major challenge for wine chemists. A number of techniques showed that the pigments were polymeric in nature. Some structures were postulated by mid-century based on reactions between anthocyanins and condensed tannin, and later postulated wine pigments were observed in model reactions. Some related compounds were then observed in wine. By the end of the 20th century, the ionization of non-volatiles for mass spectrometry opened the door to these compounds. In addition, a new class of compounds was observed, the pyranoanthocyanins, a product of fermentation and aging metabolites with anthocyanins. These compounds possess the pigment stability to SO₂ and pH change that is characteristic of aged red wine. Aging experiments show a dynamic situation with shifts in the population of pigment classes over time. The very large number of diverse pigments explains why it has been so difficult to answer the century-old question of the structure of wine pigments. Our current understanding is founded on the use of mass spectral analysis using electrospray and related ionization techniques over the last 25 years. Future progress will rely on more sophisticated analysis of this very complex mixture of substances. © 2019 Society of Chemical Industry     

Microwave dielectric properties of ultra-low loss Li2MgTi0.7(Mg1/3Nb2/3)0.3O4 ceramics sintered at low temperature by LiF addition

In this work, ultra-low loss Li₂MgTi_0.7(Mg_1/3Nb_2/3)_0.3O₄ ceramics were successfully prepared via the conventional solid-state method. X-ray photoelectron spectroscopy (XPS), thermally stimulated depolarization current (TSDC) and bond energy were used to determine the distinction between intrinsic and extrinsic dielectric loss in (Mg_1/3Nb_2/3)⁴⁺ ions substituted ceramics. The addition of (Mg_1/3Nb_2/3)⁴⁺ ions enhances the bond energy in unit cell without changing the crystal structure of Li₂MgTiO₄, which results in high Q·f value as an intrinsic factor. The extrinsic factors such as porosity and grain size influence the dielectric loss at lower sintering temperature, while the oxygen vacancies play dominant role when the ceramics densified at 1400?°C. The Li₂MgTi_0.7(Mg_1/3Nb_2/3)_0.3O₄ ceramics sintered at 1400?°C can achieve an excellent combination of microwave dielectric properties: ε_r =?16.19, Q·f?=?160,000?GHz and τ_f =??3.14?ppm/°C. In addition, a certain amount of LiF can effectively lower the sintering temperature of the matrix, and the Li₂MgTi_0.7(Mg_1/3Nb_2/3)_0.3O₄-3?wt% LiF ceramics sintered at 1100?°C possess balanced properties with ε_r?=?16.32, Q·f?=?145,384?GHz and τ_f =??16.33?ppm/°C.     

Ionic conductivities and high resolution microscopic evaluation of grain and grain boundaries of cerium-based codoped solid electrolytes

Doped CeGdO and codoped CeGdOSmO compositions were synthesized, giving rise to nanoparticulate powders. Ionic conductivities at bulk and grain boundaries of the sintered samples were determined, exhibiting increased conductivity in the samaria-codoped samples. Scanning electron microscopy (SEM) showed a significant reduction in the grain size of samaria-codoped electrolytes. This reduced grain size of the codoped samples caused a reduction in Schottky barrier height, increasing oxygen vacancy concentration in the space-charge layer of the grain boundary and culminating in greater ionic conductivity in the boundary region. For the gadolinium doped samples, high resolution transmission electron microscopy images at grains showed the presence of large cluster of defects (nanodomains), hindering the movement of charge carriers and reducing ionic conductivity. However, the samaria-codoped system displayed better homogeneity at atomic level, resulting in reduced oxygen vacancy ordering and, consequently, smaller nanodomains and higher bulk (grain) conductivity. The reduced grain sizes and smaller nanodomains caused by codoping favor the ionic conductivity of ceria-based ceramics, doped with gadolinia and codoped with samaria.     

Crosslinked quaternized poly(arylene ether sulfone) copolymer membrane applied in an electric double-layer capacitor for high energy density

The low energy density of supercapacitors, especially supercapacitors based on aqueous electrolytes, is the main factor limiting their application, and the energy density is closely related to the operating potential window of the supercapacitor. The polymer electrolyte is the main contributor to the safe operation and good ion conductivity of the supercapacitor. In this study, a crosslinked quaternized poly(arylene ether sulfone) (PAES) membrane was prepared via crosslinking during membrane formation with a thermal-only treatment and applied in an electric double-layer capacitor (EDLC). The pre-prepared PAES membrane formed a polymer electrolyte with 1 mol/L Li₂SO₄ and was then fabricated into an EDLC single cell. The properties of both the membrane and ELDC were investigated. The preferred cPAES-N-0.2 polymer electrolyte showed an ionic conductivity of 1.18 mS/cm. The optimized EDLC exhibited a single-electrode gravimetric capacitance of 104.92 F/g at a current density of 1.0 A/g and a high operating potential window (1.5 V); it, thereby, achieved a high energy density of 8.20 W h/kg. The EDLC also exhibited excellent cycling properties over 3000 charge–discharge cycles. The crosslinked structures promoted the tensile strength and thermal stability of the PAES membranes; this was accompanied by a slight decrease in the ionic conductivity. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47759.