Chemically Responsive Elastomers Exhibiting Unity‐Order Refractive Index Modulation

Chameleons are masters of light, expertly changing their color, pattern, and reflectivity in response to their environment. Engineered materials that share this tunability can be transformative, enabling active camouflage, tunable holograms, and novel colorimetric medical sensors. While progress has been made in creating artificial chameleon skin, existing schemes often require external power, are not continuously tunable, and may prove too stiff or bulky for applications. Here, a chemically tunable, large‐area metamaterial is demonstrated that accesses a wide range of colors and refractive indices. An ordered monolayer of nanoresonators is fabricated, then its optical response is dynamically tuned by infiltrating its polymer substrate with solvents. The material shows a strong magnetic response with a dependence on resonator spacing that leads to a highly tunable effective permittivity, permeability, and refractive index spanning negative and positive values. The unity‐order index tuning exceeds that of traditional electro‐optic and photochromic materials and is robust to cycling, providing a path toward programmable optical elements and responsive light routing.     

Electrochemical Impedance Spectroscopic Analysis of Sensitization-Based Solar Cells

Electrochemical impedance spectroscopy (EIS) is a very powerful tool for elucidation of charge transfer and transport processes in sensitization-based solar cells (e.g., dye-sensitized solar cells [DSSCs], quantum dot-sensitized solar cells [QDSSCs], and perovskite solar cells [PSCs]). EIS measures the electrochemical response to small amplitude AC signals over a wide range of frequencies. Analysis of the EIS response provides information about the corresponding parameters of the cells. Here, we review the fundamentals of EIS, charge transport kinetic processes, and equivalent circuit models of sensitization-based solar cells and use these concepts to explain the EIS spectra of DSSCs, QDSSCs, and PSCs. This review will be very useful for understanding the fundamental charge transfer and transport processes in different sensitization-based solar cells and the use of an equivalent circuit model to interpret the observed charge transfer and reactions.     

Multilayer assembly of ionic starches on old corrugated container recycled cellulosic fibers

In this study, old corrugated container recycled fibers were treated with polyelectrolyte multilayers consisting of biopolymer cationic starch with two degrees of substitution (DS) each in combination with one anionic starch. Pulp zeta potential, paper strength and the thin layer ellipsometry technique were applied to examine the influence of cationic starch DS on the formation of polyelectrolyte multilayers. The results indicated a significant interaction between the DS of cationic starch and the number of ionic starch layers formed. When low‐DS cationic starch was used, the pulp zeta potential and the paper strength increased significantly in assembling the first cationic layer. However, in depositing high‐DS cationic starch a greater zeta potential and a stronger influence on the paper strength were observed with a larger number of starch layers. This was confirmed by thin layer ellipsometry when a greater thickness of multilayers was achieved by employing high‐DS cationic starch to form a higher number of layers. © 2017 Society of Chemical Industry     

Oxoiron(V) Complexes of Relevance in Oxidation Catalysis of Organic Substrates

The selective oxidation of alkane and olefin moieties are reactions of fundamental importance in both chemical synthesis and biology. Nature efficiently catalyzes the oxidation of hydrocarbons using iron-dependent enzymes, which operate through the mediation of oxoiron(IV) or oxoiron(V) species. In the quest for chemo, regio and stereoselective transformations akin to those taking place in nature, bioinspired iron catalysts have been developed and understanding their mechanism of action has become a particularly relevant area of research. While a prominent advance in the preparation and characterization of oxoiron(IV) species has been accomplished, oxoiron(V) species remain exceedingly rare, presumably because the high reactivity that makes them particularly interesting also makes them difficult to observe. This review summarizes the advances in the field, focusing in synthetic systems for which the oxoiron(V) species relevant in these transformations have been directly detected and spetroscopically characterized.     

Operating limits and features of direct air capture on K2CO3/ZrO2 composite sorbent

Potassium carbonate-based sorbents are prospective materials for direct air capture (DAC). In the present study, we examined and revealed the influence of the temperature swing adsorption (TSA) cycle conditions on the CO₂ sorption properties of a novel aerogel-based K₂CO₃/ZrO₂ sorbent in a DAC process. It was shown that the humidity and temperature drastically affect the sorption dynamic and sorption capacity of the sorbent. When a temperature at the sorption stage was 29 ℃ and a water vapor pressure in the feed air was 5.2 mbar (1 bar = 10⁵ Pa), the composite material demonstrated a stable CO₂ sorption capacity of 3.4% (mass). An increase in sorption temperature leads to a continuous decrease in the CO₂ absorption capacity reaching a value of 0.7% (mass) at T = 80 ℃. The material showed the retention of a stable CO₂ sorption capacity for many cycles at each temperature in the range. Increasing P_H2O in the inlet air from 5.2 to 6.8 mbar leads to instability of CO₂ sorption capacity which decreases in the course of 3 consecutive TSA cycles from 1.7% to 0.8% (mass) at T = 29 ℃. A further increase in air humidity only facilitates the deterioration of the CO₂ sorption capacity of the material. A possible explanation for this phenomenon could be the filling of the porous system of the sorbent with solid reaction products and an aqueous solution of potassium salts, which leads to a significant slowdown in the CO₂ diffusion in the composite sorbent grain. To investigate the regeneration step of the TSA cycle in situ, the macro ATR-FTIR (attenuated total reflection Fourier-transform infrared) spectroscopic imaging was applied for the first time. It was shown that the migration of carbonate-containing species over the surface of sorbent occurs during the thermal regeneration stage of the TSA cycle. The movement of the active component in the porous matrix of the sorbent can affect the sorption characteristics of the composite material. The revealed features make it possible to formulate the requirements and limitations that need to be taken into account for the practical implementation of the DAC process using the K₂CO₃/ZrO₂ composite sorbent.     

Optical properties of epitaxial BiFeO3 thin film grown on SrRuO3-buffered SrTiO3 substrate

The BiFeO₃ (BFO) thin film was deposited by pulsed-laser deposition on SrRuO₃ (SRO)-buffered (111) SrTiO₃ (STO) substrate. X-ray diffraction pattern reveals a well-grown epitaxial BFO thin film. Atomic force microscopy study indicates that the BFO film is rather dense with a smooth surface. The ellipsometric spectra of the STO substrate, the SRO buffer layer, and the BFO thin film were measured, respectively, in the photon energy range 1.55 to 5.40 eV. Following the dielectric functions of STO and SRO, the ones of BFO described by the Lorentz model are received by fitting the spectra data to a five-medium optical model consisting of a semi-infinite STO substrate/SRO layer/BFO film/surface roughness/air ambient structure. The thickness and the optical constants of the BFO film are obtained. Then a direct bandgap is calculated at 2.68 eV, which is believed to be influenced by near-bandgap transitions. Compared to BFO films on other substrates, the dependence of the bandgap for the BFO thin film on in-plane compressive strain from epitaxial structure is received. Moreover, the bandgap and the transition revealed by the Lorentz model also provide a ground for the assessment of the bandgap for BFO single crystals.     

Tris(dithiocarbamato)iron(III) complexes as precursors for iron sulfide nanocrystals and iron sulfide-hydroxyethyl cellulose composites

Iron(III) complexes of dimethyldithiocarbamate and imidazolyl dithiocarbamate were synthesized and characterized by elemental analyses, FTIR, UV–VIS and the ligands by NMR spectroscopy. The complexes were thermolysed as single molecule precursors at 180°C to prepare octadecylamine (ODA) capped iron sulfide nanocrystals and iron sulfide-hydroxyethyl cellulose (HEC) composites. UV–VIS, PL, FTIR, P-XRD, HRTEM, FESEM and EDS were used to characterize the iron sulfide nanocrystals and corresponding HEC nanocomposites. XRD confirmed iron sulfide nanocrystal (NP1) from dimethyldithiocarbamate to be hexagonal pyrrhotite-5H, Fe₉S₁₀ crystalline phase while iron sulfide nanocrystals (NP2) from imidazolyl dithiocarbamate is in pyrrhotite, Fe₁₁S₁₂ crystalline phase. TEM images show that the iron sulfide nanocrystals have particle sizes in the range 24–32?nm for NP1 and 18–25?nm for NP2 iron sulfide nanocrystals. The optical band gaps of the iron sulfide nanocrystals obtained from Tauc plots are 3.83 and 4.16?eV for NP1 and NP2, respectively. IR spectra, FESEM surface morphology and EDS spectra of iron sulfide/HEC composites confirmed dispersion of the iron sulfide nanocrystals within the hydroxyethyl cellulose (HEC) matrix.     

Reversible Amorphous‐to‐Amorphous Transitions in Chalcogenide Films: Correlating Changes in Structure and Optical Properties

Structural transitions in materials are accompanied by appreciable and exploitable changes in physical‐chemical properties. Whereas reversible optically‐driven atomistic changes in crystal‐to‐amorphous transitions are generally known and exploited in applications, the nature of the corresponding polyamorphic transitions between two structurally distinct meta‐stable amorphous phases is an unexplored theme. Direct experimental evidence is reported for the nature of the atomistic changes during fully reversible amorphous‐to‐amorphous switching between two individual states in the non‐crystalline As₅₀Se₅₀ films prepared by pulsed‐laser deposition and consequent changes in optical properties. Combination of surface sensitive X‐ray photoelectron spectroscopy and spectroscopic ellipsometry show that the near‐bandgap energy illumination and annealing induce reversible switching in the material's structure by local bonding rearrangements. This is accompanied by switching in refractive index between two well‐defined states. Exploiting the pluralism of distinct structural states in a disordered solid can provide new insights into the data storage in emerging optical memory and photonic applications.     

A new ellipsometric approach for determining dielectric function of graphene in the infrared spectral region

Simple ellipsometric method for determining dielectric constants of absorbing two-dimensional materials on dielectric substrates is developed. The method is based on the analytical formulas obtained in the framework of a long-wave limit. An important feature of this approach lies in the fact that for data handling the problematic numerical calculation methods are not in use. The inversion problem is resolved analytically. The developed method has no need for the initial guesses of the desired parameters that is very useful from the practical point of view, for example, in the light of in-line control.     

看谱定性分析技术在铜合金中的应用

看谱定性分析与摄谱定性分析相比,其优点是简单而迅速,分析灵敏度约为0.01%～0.1%,对样品损伤小,具有设备轻便,便于搬运等特点,适用于确定某种合金的某种元素有否,对试样进行初步分析和按牌号把金属及合金进行分类分析,特别是适用于对大型工件或精密机件进行非破坏的现场分析。