Ladislav Kalvoda

Application of ab-initio molecular electronic structure calculations of radiolytic and hydrolytic stabilities of prospective extractants

For theoretical estimation of the general and local chemical stability of m-xylylene-bis-diglycolamide and its degradation products the ab-initio calculations were performed, using the Gaussian and DMol3 codes. The chemical stability was assessed according to the stability indicators, such as HOMO–LUMO gap, spatial localization of HOMO, electrostatic potential, atomic charges, and bond orders. The results of various methods are in good agreement with the published experimental stability studies. Such theoretical predictions can provide a valuable support to experimental scientists in development of novel extraction methods and stable extractants of actinide and lanthanide ions.

Development of Ammonia Gas Sensor Using Optimized Organometallic Reagent

Reliable, continuous, and spatially distributed monitoring of dangerous or irritating chemical substances belongs to standard functions of contemporary industrial and public security systems. Fiber-optic-based detection provides feasible platform to fulfill such aims. This paper deals with characterization of ammonia sensing elements based on multimode polysiloxane-clad silica-core optical fibers sensitized with 5-(4′-dioctylamino phenylimino) quinoline-8-1 cobalt bromide complex reagent immobilized into the cross-linked polymer matrix from a proper mixture of organic solvents and a radical scavenger contributing to the desired long-term stability of optical properties. The applied sensing mechanism combines optical detection principle with chemical reaction of the reagent and ammonia resulting in changes in the visible near-infrared optical absorption spectrum of the cladding layer, influencing via evanescent optical field interactions the spectral distribution of the guided light intensity. Reaction kinetics of short fiber sections exposed to ammonia/nitrogen mixture of various ammonia concentrations is tested and evaluated. The obtained sensitivity, limit of detection, and forward response time of the prepared sensors amount to ppm−1, 31 ppm, and 25 s, respectively. The obtained results are promising for fabrication of distributed fiber-optic sensors applicable to detection and location of ammonia gas leaks in industrial as well as general public premises.

Development of absorption fiber optic sensor for distributed measurement of ammonia gas

Polymer-clad silica optical fibers are employed for development of different absorption optic fiber sensors of gaseous analytes. In our case, the physical principles of the detection are combined with a chemical reaction between analyte and suitable opto-chemical absorption reagents. Selected organometallic complex reagents with different lengths of lateral aliphatic chains are studied with respect to the type of central ions and their coordinative conditions to surrounding ligands. The effect of solvent type on solubility and the long-term stability of the prepared reagents in solid matrix are presented and discussed. Various methods are also tested in order to achieve an effective reagent immobilization into the polymer matrix, which creates optical fiber cladding. The chemical reaction of the reagents with ammonia based on ligand exchange process is accompanied by changes of visible-near-infrared optical absorption influencing via evanescent field on the guided light intensity. Experimental results suggest that the selected reagents provide optical properties suitable for practical sensing applications and that the sensitized PCS optical fibers could be used for detection of ammonia gas.

Neutronographic Texture Analysis of Zirconium Based Alloys

Neutron diffraction is a very powerful tool in texture analysis of zirconium based alloys used in nuclear technique. Textures of five samples (two rolled sheets and three tubes) were investigated by using basal pole figures, inversion pole figures, and ODF distribution function. The texture measurement was performed at diffractometer KSN2 on the Laboratory of Neutron Diffraction, Department of Solid State Engineering, Faculty of Nuclear Sciences and Physical Engineering, CTU in Prague. Procedures for studying textures with thermal neutrons and procedures for obtaining texture parameters (direct and inverse pole figures, three dimensional orientation distribution function) are also described. Observed data were processed by software packages HEXAL and GSAS. Our results can be summarized as follows: i) All samples of zirconium alloys show the distribution of middle area into two maxima in basal pole figures. This is caused by alloying elements. A characteristic split of the basal pole maxima tilted from the normal direction toward the transverse direction can be observed for all samples, ii) Sheet samples prefer orientation of planes (100) and (110) perpendicular to rolling direction and orientation of planes (002) perpendicular to normal direction, iii) Basal planes of tubes are oriented parallel to tube axis, meanwhile (100) planes are oriented perpendicular to tube axis. Level of resulting texture and maxima position is different for tubes and for sheets. The obtained results are characteristic for zirconium based alloys.

Sensing applications of U-optrodes

Preparation of refractometric, thermometric and chemo-optical sensing heads based on extremely curved optical fibers (U-optrodes) is described and their sensing properties demonstrated on obtained experimental results.

Structure and texture analysis of PVC foils by neutron diffraction

Crystalline order of molded and then bi-axially stretched foils prepared from atactic PVC resin is investigated by means of wide-angle neutron diffraction (WAND). The observed high-resolution WAND patterns of all samples are dominated by a sharp maximum corresponding to the inter-planar distance 0.52 nm. Two weaker maxima are also resolved at 0.62 and 0.78 nm. Intensities of the peaks vary with deformation ratios of the samples and their diffraction position. Average size of the coherently scattering domains is estimated as approximately 4-8 nm. Based on the experimental data, a novel model of crystalline order of atactic PVC is proposed.

Texture Investigations of Zircaloy-4 Tubes by Neutron Diffraction

This article presents the results of texture investigations of Zircaloy-4 tubes. Neutron diffraction and inversion pole figures were used to chracterize the texture of samples. The main interest is given to the analysis of texture changes under different tensile test conditions including tensile force direction, annealing temperature and tensile test temperature. Four different specimens of different orientation to the tube axis were tested.

Texture Analysis of Poly(vinyl Chloride) Foils

The crystallographic textures of the free-standing diamond films which were synthesized by the chemical vapor deposition (CVD) using a CH4/H2/Ar gas mixtures have been investigated. Texture components of the diamond films are analyzed with pole figures and orientation distribution function (ODF). The surface morphology of the diamond films grown at different substrate temperatures as well as different gas concentrations is observed with scanning electron microscopy.(SEM). The experimental results indicate that the intensity of {110} fibre texture becomes much higher with the increase of the substrate temperature. It is considered that the higher multiplicity of <110> crystallographic direction in diamond octahedron leads to the higher appearance possibility of {110} fibre texture and the final texture components of the diamond films depend upon the CVD deposition parameters.

PREPARING OF THE CHAMELEON COATING BY THE ION JET DEPOSITION METHOD

Preparation of chameleon coatings using an Ionized Jet Deposition (IJD) technique is reported in the present paper. IJD is a new flexible method for thin film deposition developed by Noivion, Srl. The chameleon coatings are thin films characterised by a distinct change of their tribological properties according to the external conditions. The deposited films of SiC and TiN materials were examined by the Raman spectroscopy, SEM and XPS. The results of the Raman spectroscopy have proved an amorphous structure of SiC films. The data from XPS on TiN films have shown that the films are heavily oxidized, but also prove that the films are composed of TiN and pure Ti. The SEM provided information about the size of grains and particles constituting the deposited films, which is important for tribological properties of the films. Deposition of the chameleon coating is very complex problem and IJD could be ideal method for preparation of this coating.

Diffusion of ammonia gas in PDMS characterized by ATR spectroscopy

The kinetic parameters of a chemo-optical transducer layer sensitive to gaseous ammonia are characterized by means of attenuation total reflection method. The tested layer consists of cross-linked polydimethylsiloxane matrix sensitized by quinoline-based organometallic dye showing the selective chemical reaction with ammonia. Upper and lower limits of the ammonia diffusion coefficient and the ammonia-dye reaction constant are derived from the obtained experimental data and compared with other data available in literature and obtained from computer simulations.