Polarization-maintaining reflection-mode THz time-domain spectroscopy of a polyimide based ultra-thin narrow-band metamaterial absorber

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

Molecular degradation of ancient documents revealed by 1H^1H HR-MAS NMR spectroscopy

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these products can catalyze further degradation, their knowledge is fundamental to improve conservation strategies of historical documents.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

Confocal Imaging at 0.3 THz with depth resolution of a painted wood artwork for the identification of buried thin metal foils

A compact confocal terahertz microscope working at 0.30 THz based on all-solid-state components is used to locate buried thin metal foils in a painted wood artwork. Metal foils are used for decoration, and their precise localization under the pictorial layer is relevant information for conservation scientists and restorers, which can neither be obtained by X-ray radiography nor by spectroscopic imaging in the infrared, as we directly show here. The confocal microscopy principle based on the spatial pinhole concept is here implemented by positioning the first focus of an ellipsoidal reflector at the phase center of horn antennas coupled to Schottky diode detector and emitter mounted in rectangular waveguide blocks, together with an optical beamsplitter. The second focus of the reflector is mechanically scanned inside the sample in three dimensions. The predictions of diffraction theory for a confocal microscope at an imaging wavelength of 1.00 mm with numerical aperture of 0.53 are verified experimentally (1.2 and 2.8 mm for the lateral and the axial resolution, respectively). These values of resolution allow a precise determination of the position of buried metal foils in an ancient piece of art hence making restoration interventions possible

Temperature behavior of optical absorption bands in colored LiF crystals

We measured the optical absorption spectra of thermally treated, gamma irradiated LiF crystals, as a function of temperature in the range 16–300 K. The temperature dependence of intensity, peak position and bandwidth of F and M absorption bands were obtained. Keywords: Lithium fluoride, Optical absorption, Low temperature, Color center

CuO nanoparticles and microaggregates: an experimental and computational study of structure and electronic properties

The link between morphology and properties is well-established in the nanoparticle literature. In this report, we show that different approaches in the synthesis of copper oxide can lead to nanoparticles (NPs) of different size and morphology. The structure and properties of the synthesized NPs are investigated with powder X-ray diffraction, scanning electron microscopy (SEM), and diffuse reflectance spectroscopy (DRS). Through detailed SEM analyses, we were able to correlate the synthetic pathways with the particles’ shape and aggregation, pointing out that bare hydrothermal pathways yield mainly spheroidal dandelion-like aggregates, whereas, if surfactants are added, the growth of the nanostructures along a preferential direction is promoted. The effect of the morphology on the electronic properties was evaluated through DRS, which allowed us to obtain the electron bandgap in every system synthesized, and to find that the rearrangement of threaded particles into more compact structures leads to a reduction in the energy difference. The latter result was compared with Density Functional Theory (DFT) computational models of small centrosymmetric CuO clusters, cut from the tenorite crystal structure. The computed UV-Vis absorption spectra obtained from the clusters are in good agreement with experimental findings

Room temperature syntheses of ZnO and their structures

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 (TP) and a drying (TD) temperature of 40 ◦C. Higher temperatures also afforded ZnO, but lowering any of the TP or TD 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 TP = TD = 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 TP = 50 ◦C, TD = 40 ◦C, or TP = TD = 60 ◦C, respectively. At TP = TD = 30 ◦C, micrometric structures aggregated in foils are obtained, which segregate nanoparticles of ZnO if TD 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

Experimental and theoretical study of the yellowing of ancient paper

Paper is the most widely used writing support due to the remarkable properties of its principal component - cellulose - one of the most abundant biomaterials present on Earth. However, due to the complexity of the material, an exhaustive picture of its degradation pathways is still missing. In this paper, we will present recent results and progresses obtained in the comprehension of the role of cellulose oxidation in the yellowing of ancient paper. Visible and ultraviolet spectra of cellulose in ancient paper samples and reference modern samples artificially aged have been interpreted with the aid of ab-initio Time-Dependent Density Functional Theory calculations. Through the comparison of measured and calculated absorption spectra, several oxidized forms of cellulose polymers, acting as chromophores, and responsible for ancient paper yellowing were identified. The relative concentration of ketones and aldehydic groups depends on the environmental conditions in which samples were stored along their life

Molecular origin of the two-step mechanism of gellan aggregation

Among hydrocolloids, gellan is one of the most studied polysaccharides due to its ability to form mechanically stable gels. Despite its long-standing use, the gellan aggregation mechanism is still not understood because of the lack of atomistic information. Here, we fill this gap by developing a new gellan force field. Our simulations offer the first microscopic overview of gellan aggregation, detecting the coil to single-helix transition at dilute conditions and the formation of higher-order aggregates at high concentration through a two-step process: first, the formation of double helices and then their assembly into superstructures. For both steps, we also assess the role of monovalent and divalent cations, complementing simulations with rheology and atomic force microscopy experiments and highlighting the leading role of divalent cations. These results pave the way for future use of gellan-based systems in a variety of applications, from food science to art restoration