National Institute Of Materials Physics - Romania

Hybrid bionanocomposite coating systems (HBCSs) are green polymer materials consisting of an interface between a coating matrix and nanoparticles. The coating matrix was prepared by using a nonisocyanate poly(hydroxyl urethane) (NIPHU) prepolymer crosslinked via 1,3-diaminopropane and epoxidized Jatropha curcas oil. TEMPO-oxidized cellulose nanoparticles (TARC) were prepared from microcrystalline cellulose, and (3-aminopropyl)trimethoxysilane (APTMS)-coated ZnO nanoparticles (APTMS-ZnO) and their suspensions were synthesized separately. The suspensions at different weight ratios were incorporated into the coating matrix to prepare a series of HBCSs. FT-IR, H-1-NMR, C-13-NMR, XRD, SEM, and TEM were used to confirm the chemical structures, morphology, and elements of the coating matrix, nanomaterials, and HBCSs. The thermomechanical properties of the HBCSs were investigated by TGA-DTG and pencil hardness analyses. The UV and IR absorption spectra of the HBCSs were obtained using UV-vis spectroscopy and FTIR spectroscopy, respectively. The HBCSs exhibited good thermal stability at about 200 degrees C. The degradation temperature at 5% mass loss of all samples was over around 280 degrees C. The HBCSs exhibited excellent UV block and IR active properties with a stoichiometric ratio of the NIPHU prepolymer and EJCO of 1:1 (wt/wt) containing 5 wt % TARC and 15 wt % APTMS-ZnO nanoparticles. It was observed that the sample with 5 wt % TARC and 15 wt % APTMS-ZnO (HBCS-2) exhibited a uniform crosslinking and reinforcement network with a T-onset of 282 degrees C. This sample has successfully achieved good coating hardness and excellent UV and IR absorption.

The aim of this paper is the study of the thermal behavior of the simonkolleite Zn-5(OH)(8)Cl-2 center dot H2O (ZHC) by electron paramagnetic resonance (EPR) spectroscopy, in particular. It is well known that during heating ZHC undergoes a complex transformation which involves several overlapping stages. However, with reference to the data reported on this subject, it can be concluded that there is still an ongoing debate regarding the intermediate stages of this process. The data presented in this study support a simple decomposition process of the ZHC prepared using the precipitation method. The EPR data correlated to the data obtained by other experimental techniques, such as XRD, TEM, SEM and EDX, indicate that during the thermal treatment the ZHC suffers a partial decomposition to ZnO with no intermediate products. After annealing at 500 degrees C for 1 h, a recombination process of ZHC is observed. Moreover, the kinetics associated to these decomposition steps were determined and the evolution of the paramagnetic centers was also followed and studied. This study offers new information related to the thermal behavior of ZHC, especially regarding the EPR data which is reported for the first time on this subject and material.

Germanium Metal-Ferroelectric-Semiconductor (MFS) capacitors based on ferroelectric Hf1-xZrxO2 (HZO) with clean, oxide free Ge/HZO interfaces emerge as an interesting layer structure for the fabrication of ferroelectric field effect transistor (FeFET) non-volatile memory devices. It is shown that, at low temperature (<160K), a semiconductor depletion forms in Ge near the interface, resulting in an increase in coercive voltage by about 2V, accompanied by a distortion of the ferroelectric hysteresis with subloop asymmetric behavior, which becomes more severe at higher frequencies of measurement. At higher temperatures, the Ge surface near the ferroelectric is easily inverted due to the low energy gap of Ge, providing sufficient screening of the polarization charge by minority free carriers, in which case, nearly ideal, symmetric hysteresis curves are recovered. The depolarization field is experimentally extracted from the coercive voltage and the capacitance measurements, is found to be 2.2MV/cm in the low temperature range, comparable to the coercive field, then rapidly decreases at higher temperatures, and effectively diminishes at room temperature. This makes Ge MFSs good candidates for FeFETs for low voltage non-volatile memory with improved reliability.

Molecular mobility of cyanophenyl alkylbenzoates (CPnBs) (n = 2, 3, 7 - number of carbon atoms in the alkyl chain) in the bulk and in composites with aerosil A380 is investigated by broadband dielectric spectroscopy, while thermal analysis and infrared spectroscopy were applied to characterise the molecular species. The work completes preliminary results obtained for the members with n = 4 ... 6. An interaction by hydrogen bonding, between aerosil surface - OH groups and - CN or ester groups of the CPnB molecules takes place. It slows down the relaxation process as observed for related composites in comparison to the pure materials. The existence of two types of bonding might be the reason that Vogel temperature for the relaxation process in the surface layer does not show the odd-even effect. Temperature dependence of the relaxation rates for composites shows a crossover behaviour from a high to a low temperature regime. Moreover, the temperature dependence of the dielectric strength is unusual. As the loading degree is similar, comparison of the dielectric, spectroscopic and thermal data obtained here and with the results obtained for the composites with n = 4 ... 6 can be directly done. Increasing the number of the members of the homologous series confirms and hardens the preliminary conclusions.

Formation of SiGe nanocrystals in an oxide matrix via deposition and subsequent annealing is a widely applied approach as it gives good control over optical properties by varying the Ge atomic fraction, the size, shape and crystallinity of the nanocrystals. A common drawback of annealing is a strain relaxation in the structure creating dislocations, point defects, dangling bonds, Ge clustering and altered interface morphology. All these phenomena are well-known to degrade the optoelectronic and electrical properties of the structure. As a proof of concept, in this study we have utilized a modern technique of high impulse power magnetron sputtering (HiPIMS) to obtain a crystalline TiO2/SiGe/TiO2 structure without any pre-/post-annealing. It is furthermore demonstrated how a control of the nano-crystallite size is obtained by altering the HiPIMS discharge power alone. Grazing incidence X-ray diffraction analysis was carried out for the structural characterization, while photocurrent measurements were utilized to access the role of TiO2 structural morphology over interface integrity in determining spectral feature and sensitivity. An increase of 1 - 2 orders magnitude in spectral intensity was achieved for as-grown structures fabricated via HiPIMS in comparison to annealed structure, sputtered with conventional direct current magnetron sputtering.

The pyroelectric coefficient of some Pb(Zr,Ti)O-3 type ceramics was estimated using two methods: a direct method, based on the temperature dependence of the charge/current generated by pyroelectric effect; an indirect method based on the frequency dependence of the pyroelectric signal generated by a pyroelectric element under modulated irradiation with infrared light. The purpose was to compare the results and to assess if the indirect method is enough accurate for rapid estimation of the pyroelectric coefficient of a material envisaged for infrared detection. The direct method is more accurate and requires accurate control of temperature and heating rate, while the indirect method is less accurate, with an error up to 20%, and requires the knowledge of quantities such as dielectric constant, electric conductance, and incident power. However, the indirect method can be more easily implemented and can provide a rapid assessment on the pyroelectric quality of a material with potential use in infrared detectors.

Mesoporous CeO2:Mn3O4 materials (3:7 and 7:3 molar ratio) were prepared by co-precipitation and deposited as porous thick films over alumina (Al2O3) planar substrate provided with Pt meander. The aim was oriented towards detecting low levels methane (CH4) at moderate operating temperatures. Herein we demonstrated that the sensitivity of catalytic micro-converters (CMCs) towards a given peak of CH4 concentration corresponds to specific gas-surface interaction phenomena. More precisely, a transition from thermal conductivity to combustion rate is likely to occur when CMCs are operated under real atmospheric conditions (normal pressure, presence of relative humidity, and constant operating temperature). The response to CH4 was analyzed over different gas flows and different gas concentrations under the same operating regime. The materials were fully characterized by adsorption-desorption isotherms, H-2-Temperature Programmed Reduction (H-2-TPR), X-ray Diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Scanning Electron Microscopy (SEM), and Raman spectroscopies. Thus, the applicative aspect of using CeO2:Mn3O4 as moderate temperature CMC for CH4 detection is brought to the fore.

In this work, new optical properties of composites based on polystyrene (PS) microspheres and graphene oxide (GO) are reported. The radical polymerization of styrene in the presence of benzoyl peroxide, pentane and GO induces the appearance of new ester groups in the PS macromolecular chains remarked through an increase in the absorbance of the infrared (IR) band at 1743 cm(-1). The decrease in the GO concentration in the PS/GO composites mass from 5 wt.% to 0.5 wt.% induces a diminution in the intensities of the D and G Raman bands of GO simultaneous with a down-shift of the D band from 1351 to 1322 cm(-1). These variations correlated with the covalent functionalization of the GO layers with PS. For the first time, the photoluminescent (PL) properties of PS/GO composites are reported. The PS microspheres are characterized by a PL band at 397 nm. Through increasing the GO sheets' concentration in the PS/GO composite mass from 0.5 wt.% to 5 wt.%, a PS PL quenching process is reported. In addition, in the presence of ultraviolet A (UVA) light, a photo-degradation process of the PS/GO composite having the GO concentration equal to 5 wt.% is demonstrated by the PL studies.

This work involves the synthesis and characterization of Cu2ZnSnS4 (CZTS) layers. The films were prepared on Mo/glass substrates by single-step electrodeposition method followed by sulfurization at 500 degrees C under argon flow. The effect of boric acid concentration on the crystallographic structure, compositional and morphological properties of CZTS films was investigated, with the objective to understand the growth behavior and to enhance the film properties. Cyclic Voltammetry was used in order to estimate the adequate deposition potential for the CZT alloy. The x-ray diffraction analysis showed the formation of the kesterite phase in all the samples. The Raman and x-ray photoelectron spectroscopy studies confirmed the existence of the CZTS phase. The scanning electron microscopy was employed to inspect the films structure. The results indicated that increasing the concentration of boric acid affects the physico-chemical properties of the films.

Grain boundaries, twins, and defects are considered to influence the thermomechanical behavior of any covalent ceramic, as a result, monolithic B4C samples show different curve shapes of bending strength vs temperature and the present theoretical models fail to fit them over the entire temperature range. To overcome these issues, we fabricated a novel high-density boron carbide and evaluated its high-temperature bending strength. The as-obtained ceramic is composed of boron carbide grains and a fine grain-boundary metal Pt framework. The material shows a decreased strength, which is due to a non-linear increase in the volume expansion coefficient of the B4C. Recovery in strength above 1000 degrees C is due to the presence of twins, their growth and rearrangements. We consider twins rearrangements are the pieces of evidence for a novel 'micro' mechanism of high-temperature stress accommodation for the boron carbide bulks.