This paper reports the design, the microfabrication and the experimental characterization of an ultra-thin narrow-band metamaterial absorber at terahertz frequencies. The metamaterial device is composed of a highly flexible polyimide spacer included between a top electric ring resonator with a four-fold rotational symmetry and a bottom ground plane that avoids misalignment problems. Its performance has been experimentally demonstrated by a custom polarization-maintaining reflection-mode terahertz time-domain spectroscopy system properly designed in order to reach a collimated configuration of the terahertz beam. The dependence of the spectral characteristics of this metamaterial absorber has been evaluated on the azimuthal angle under oblique incidence. The obtained absorbance levels are comprised between 67% and 74% at 1.092 THz and the polarization insensitivity has been verified in transverse electric polarization. This offers potential prospects in terahertz imaging, in terahertz stealth technology, in substance identification, and in non-planar applications. The proposed compact experimental set-up can be applied to investigate arbitrary polarization-sensitive terahertz devices under oblique incidence, allowing for a wide reproducibility of the measurements.

Artifacts made of cellulose, such as ancient documents, pose a significant experimental challenge in the terahertz transmission spectra interpretation due to their small optical thickness. In this paper, we describe a method to recover the complex refractive index of cellulose fibers from the terahertz transmission data obtained on single freely standing paper sheets in the (0.2–3.5)-THz range. By using our technique, we eliminate Fabry-Perot effects and recover the absorption coefficient of the cellulose fibers. The obtained terahertz absorption spectra are explained in terms of absorption peaks of the cellulose crystalline phase superimposed to a background contribution due to a disordered hydrogen-bond network. The comparison between the experimental spectra with terahertz vibrational properties simulated by density-functional-theory calculations confirms this interpretation. In addition, evident changes in the terahertz absorption spectra are produced by natural and artificial aging on paper samples, whose final stage is characterized by a spectral profile with only two peaks at about 2.1 and 3.1 THz. These results can be used to provide a quantitative assessment of the state of preservation of cellulose artifacts.

For centuries mankind has stored its knowledge on paper, a remarkable biomaterial made of natural cellulose fibers. However, spontaneous cellulose degradation phenomena weaken and discolorate paper over time. The detailed knowledge of products arising from cellulose degradation is essential in understanding deterioration pathways and in improving durability of cultural heritage. In this study, for the first time, products of cellulose degradation were individually detected in solid paper samples by means of an extremely powerful proton HR-MAS NMR set-up, in combination to a wise use of both ancient and, as reference, artificially aged paper samples. Carboxylic acids, in addition to more complex dicarboxylic and hydroxy-carboxylic acids, were found in all samples studied. Since these products can catalyze further degradation, their knowledge is fundamental to improve conservation strategies of historical documents. Furthermore, the identification of compounds used in ancient production techniques, also suggests for artifacts dating, authentication and provenance.

ZnO has many technological applications which largely depend on its properties, which can be tuned by controlled synthesis. Ideally, the most convenient ZnO synthesis is carried out at room temperature in an aqueous solvent. However, the correct temperature values are often loosely defined. In the current paper, we performed the synthesis of ZnO in an aqueous solvent by varying the reaction and drying temperatures by 10 °C steps, and we monitored the synthesis products primarily by XRD). We found out that a simple direct synthesis of ZnO, without additional surfactant, pumping, or freezing, required both a reaction (T_P) and a drying (T_D) temperature of 40 °C. Higher temperatures also afforded ZnO, but lowering any of the T_P or T_D below the threshold value resulted either in the achievement of Zn(OH)₂ or a mixture of Zn(OH)₂/ZnO. A more detailed Rietveld analysis of the ZnO samples revealed a density variation of about 4% (5.44 to 5.68 gcm⁻³) with the synthesis temperature, and an increase of the nanoparticles’ average size, which was also verified by SEM images. The average size of the ZnO synthesized at T_P = T_D = 40 °C was 42 nm, as estimated by XRD, and 53 ± 10 nm, as estimated by SEM. For higher synthesis temperatures, they vary between 76 nm and 71 nm (XRD estimate) or 65 ± 12 nm and 69 ± 11 nm (SEM estimate) for T_P = 50 °C, T_D = 40 °C, or T_P = T_D = 60 °C, respectively. At T_P = T_D = 30 °C, micrometric structures aggregated in foils are obtained, which segregate nanoparticles of ZnO if T_D is raised to 40 °C. The optical properties of ZnO obtained by UV-Vis reflectance spectroscopy indicate a red shift of the band gap by ~0.1 eV.

In the present paper, we investigate the effects of alkali and operational temperature on NiO capacitive and optical properties. The NiO samples were prepared by a straightforward, surfactant-free hydrothermal synthesis, employing Ni(NO₃)₂ and either urea or moderately sterically hindered triethylamine (TEA). The syntheses were followed by calcinations at either 400 or 600 °C. NiO samples were characterized by XRD, scanning electron microscopy, and nitrogen adsorption isotherms. The optical properties were investigated by reflectance spectroscopy, and the pseudocapacitance was studied by cyclic voltammetry and galvanostatic charge charge-discharge measurements. We found that the synthesis with TEA yielded nanoflowers whereas the morphology of the synthesis with urea varied with the calcination temperature and resulted in nanoparticles or nanoslices at calcination temperatures of 400 and 600 °C, respectively. The NiO samples prepared at a lower temperature displayed a favorable combination of surface area and porosity that allowed for high performance with capacitances of 502 and 520 F g⁻¹ at a current density of 1 A g⁻¹ for nanoflowers and nanoparticles, respectively. The band gaps of all the samples were compatible with the estimated nanoparticle sizes. Finally, we used the synthesized NiO samples for the preparation of screen-printed electrodes (SPEs) modified by drop-casting and probed them against a [Fe(CN)₆]^3−/4− probe.