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Silylation of cellobiose as a model reaction for the synthesis of silylated cellulose : a DFT and PM3 approach
Stefan Spirk, Heike Ehmann, Volker Ribitsch, Karin Stana-Kleinschek, 2011, objavljeni znanstveni prispevek na konferenci

Opis: The object of the present study is the isodesmic reaction of cellobiose (the repeating unit in cellulose) with different kinds of silanes, R-SiH3, to form silylated cellobiose (Cello-SiH3) and the corresponding alcohols (R-OH). The size and the chemical reactivity of the substituent R is varied as well as the position where O-silylation at the cellobiose takes place. In contrast to experimental observations where the O6 position is favored for silylation, for the computed reactions, energy differences are smaller than 3 kcal/mol for the different positions at the B3LYP/6-311G* as well as at the B3LYP/6-311+G* level of theory. Depending on the silane, reaction energies in a range from -17 kcal/mol (R=NHSiH3) and +18 kcal/mol (R=F) have been calculated. In addition, semi-empirical calculations on the PM3 level of theory have been performed. These results are set into contrast with the results derived from DFT calculations to assess whether semi-empirical methods may be useful for the description of larger systems containing silylated cellobiose units.
Ključne besede: silylation of cellobiose, silanes, DFT, PM3
Objavljeno: 01.06.2012; Ogledov: 841; Prenosov: 4
URL Polno besedilo (0,00 KB)

Analysis of the oxidation of cellulose fibres by titration and XPS
Lidija Fras, Leena Sisko Johansson, Peer Stenius, Janne Laine, Karin Stana-Kleinschek, Volker Ribitsch, 2005, izvirni znanstveni članek

Opis: The purpose of this study was to evaluate the effect of selective oxidation on the surface properties of cotton cellulose fibres. Four different methods to evaluate the accessibility, nature and content of ionisable acidic groups (charge) in the fibres were applied: potentiometric and conductometric titrations, polyelectrolyte adsorption and X-ray photoelectron spectroscopy (XPS). The results from this combination of methods show that two processes take place when the oxidation method is applied: elimination of low molecular mass non-cellulosic compounds and formation of new acidic groups in the cellulose chains. Which of these processes is predominating depends on oxidation time, but the first one is initially more important. Polyelectrolyte adsorption and XPS show that the surface concentration of acidic groups is considerably lower than the bulk concentration, i.e. during oxidation the content of carboxyl groups in the surface region decreases, while it increases in amorphous regions. The decrease is due to the dissolution of low molecular weight compounds; the increase is due to the formation of new acidic groups. The use of titration methods in combination with XPS appears to be a very useful tool for identification of the formation and distribution of ionic groups in cotton fibres and their surfaces.
Ključne besede: textile fibres, cotton fibres, cellulose fibres, oxidation, X-ray photoelectron spectroscopy, XPS, acid groups in fibres
Objavljeno: 01.06.2012; Ogledov: 860; Prenosov: 5
URL Polno besedilo (0,00 KB)

The interaction ability of cellulosic materials as a function of fine structure and Helmholtz surface energy
Tatjana Kreže, Karin Stana-Kleinschek, Volker Ribitsch, Zdenka Peršin, Majda Sfiligoj-Smole, 2005, izvirni znanstveni članek

Opis: Many chemical or physical modification processes significantly influence the accessibility of fiber forming polymers by causing structural changes. The wettability and sorption ability improvements of polymeric materials are major tasks during finishing processes. Different pre-treatment processes are used in order to improve the accessibility of dissociable groups, hydrophilicity, dyeability, and whiteness. These are usually alkaline purification, chemical bleaching and mercerization. In a previous paper we presented the data for structural characteristics (density, crystallinity index, molecular orientation, void volume, diameter and the specific inner surface of void, etc.) of untreated regenerated cellulose fibers (viscose, modal and lyocell) [41]. We now compare the influence of different pre-treatment processes on fiber structure and the accessibility of the chemical groups of these fibers. In order to improve the accessibility, two pre-treatment processes were used: chemical bleaching of fibers and tensionless alkali treatment. The influence of these pre-treatment processes on the structure parameters was evaluated using viscosity measurements (determination of polymerization degree (DIN 54 270)) and iodine sorption ability measurements according to the Schwertassek method (determination of crystallinity index) [13, 16]. The reactivity and accessibility in a polar environment was determined using tensiometry. Contact angles between the fibers and liquids of different polarities were determined using the powder contact angle method and calculated from a modified Washburn equation [26, 28]. The surface free (Helmholtz) energy of differently treated fibers was determined from the contact angle data using the Owens-Wendt-Raeble-Kaelble approximation [30, 33, 35]. The differences in the accessibility of raw and pre-treated regenerated cellulose fibers obtained using tensiometry are compared with the results of the conventional method used to determine moisture adsorption (DIN 54 351, DIN 53 802). In regard to raw fibers, viscose shows the most hydrophilic characteristic: adsorbs the highest amount of moisture, has the fastest penetration velocities (Fig. 6), the smallest contact angle, and the highest SFE (Fig. 8). Modal fibers have the largest contact angle, the lowest SFE, and they adsorb the smallest amount of water vapor. Pre-treatments increase the sorption ability and the surface free (Helmholtz) energy while they decrease the contact angle. This makes the material more accessible to water and chemicals used in the finishing processes although the crystallinity index increases. The main modification in polymer properties caused by the treatments is an increase in the fiber SFE caused by an increase of the fiber surfaces because of swelling in the alkaline medium (washing, slack-mercerization), and due to an increase of accessible OH- and COOH-groups (bleaching). This enables the formation of an increased number of hydrogen bridges between the water molecules and the OH- and COOH-groups. Our investigations confirm the results published earlier thatthe main property necessary for the proper sorption behavior of cellulose materials are the accessible, less ordered regions and not the degree of crystallinity.
Ključne besede: regenerated cellulose fibers, fiber pre-treatment, iodine sorption, cristallinity, tensiometry, contact angle, Helmholtz surface energy, water adsorption
Objavljeno: 01.06.2012; Ogledov: 1209; Prenosov: 5
URL Polno besedilo (0,00 KB)

Electrokinetic investigation of polyelectrolyte adsorption and multilayer formation on a polymer surface
Stefan Köstler, Volker Ribitsch, Karin Stana-Kleinschek, Georg Jakopic, Simona Strnad, 2005, izvirni znanstveni članek

Opis: Self assembled polyelectrolyte layers of poly(sodium 4-styrenesulfonate) (PSS), and poly(diallyldimethylammonium chloride) (PDADMAC) were deposited on planar poly(ethylene terephthalate) (PET) substrates using the layer-by-layer technique. Charged functional groups were generated on the polymer substrates by means of a surface modification procedure prior to polyelectrolyte adsorption. The layers were characterised concerning their electrokinetic properties. The build-up of multilayer architectures could be followed by changes of the zeta-potential versus pH curves. An increase of coating density with increasing layer number was found. The electrokinetic properties of the PET substrates were not recognised anymore if more then four layers were applied. If PSS formed the outermost layer these assemblies were very stable against shear forces while if PDADMAC formed the outermost layer the films were partially destroyed by high shear forces.
Ključne besede: textile materials, polyelectrolyte multilayers, layer-by-layer assembly, zeta-potential, ellipsometry, polymer substrate, layer stability
Objavljeno: 01.06.2012; Ogledov: 910; Prenosov: 3
URL Polno besedilo (0,00 KB)

Substrate-induced coagulation (SIC) of nano-disperse titania in non-aqueous media : the dispersibility and stability of titania in N-methyl-2-pyrrolidinone
Angelika Basch, Simona Strnad, Volker Ribitsch, 2009, izvirni znanstveni članek

Opis: Dispersions of 1 wt% titandioxide (titania or TiO2) were investigated with respect to their stability in non-aqueous media. The objective of this work was to find conditions for the substrate-induced coagulation (SIC) process in N-methyl-2-pyrrolidinone (NMP). The SIC process is a dip-coating process that enhances adsorption of fine dispersed particles on a pre-conditioned surface. The wetting behavior of titania and NMP was investigated by the powder contact angle method. The absorption process of the polar solvent NMP on the acid oxide TiO2and Aerosol OT (AOT) (bis-2-ethylhexyl sodium sulfosuccinate) was also investigated and a polar or hydrophilic interaction was found. The stability of titania in NMP dispersions and the influence of the solvent AOT and the electrolyte LiCl was investigated. By studying the electrophoretic mobilities of titania particles in NMP and the influence on solutes by the electrophoretic method phase analysis light scattering (PALS) and the electroacoustic method this paper explores suitable conditions for non-aqueous substrate-induced coagulation of titania.
Ključne besede: contact angle, non-aqueous dispersions, electrophoretic mobilities, substrate-induced coagulation, titandioxide, zeta potential
Objavljeno: 01.06.2012; Ogledov: 750; Prenosov: 2
URL Polno besedilo (0,00 KB)

Adsorption of fucoidan and chitosan sulfate on chitosan modified PET films monitored by QCM-D
Tea Indest, Janne Laine, Leena Sisko Johansson, Karin Stana-Kleinschek, Simona Strnad, Renate Dworczak, Volker Ribitsch, 2009, izvirni znanstveni članek

Opis: The adsorption behavior of fucoidan as well as chitosan derivatives (chitosan sulfate) on poly(ethylene terephthalate) (PET) model film surface was studied using the quartz crystal microbalance technique. These systems were chosen for this study due to their promising biocompatible properties. Moreover, fucoidan and chitosan sulfate have promising anticoagulant properties and represent an alternative to heparin treatment of vascular grafts. As a first step, PET foils were activated by alkaline hydrolysis to increase their hydrophilicity. From these foils, model PET films were prepared by the spin coating technique on a silica quartz crystal. The selected polysaccharides (chitosan, fucoidan, and chitosan sulfate) were adsorbed from aqueous solutions on the PET surfaces. The adsorption was monitored using a quartz crystal microbalance with a dissipation unit. The surface chemistry and morphology of the chitosan/fucoidan or chitosan/chitosan sulfate coated PET-H films was analyzed using XPS and AFM. It was found that chitosan/fucoidan films were thinner and more compressed, while in the case of chitosan/chitosansulfate, large amounts of chitosan sulfate were adsorbed, indicating a loose and thick adsorbed film.
Ključne besede: PET films, fucoidan, chitosan sulfate, adsorption, anticoagulant properties
Objavljeno: 01.06.2012; Ogledov: 758; Prenosov: 3
URL Polno besedilo (0,00 KB)

X-ray study of pre-treated regenerated cellulose fibres
Majda Sfiligoj-Smole, Zdenka Peršin, Tatjana Kreže, Karin Stana-Kleinschek, Volker Ribitsch, Susanne Neumayer, 2003, izvirni znanstveni članek

Opis: Regenerated cellulose fibres have had an important role to play in the man-made fibre field. The very special characteristics of different types of regenerated cellulose fibres, e.g. mechanical properties, sorption characteristics, and aesthetics were conditioned by the differences in their fine structure due to fibre formation processes. Additionally, the finishing processes could influence the fibre structure. A study was done of the crystalline structures of a solvent-spun cellulose fibre type (Lenzing Lyocell), made according to the NMMO process, and two conventional cellulosic fibre types, made by the viscose process (Lenzing Viscose and Lenzing Modal). The fibres were pre-treated (bleached and slack mercerised) and structural changes were followed by wide angle and small angle x-ray scattering (WAXS and SAXS), respectively. The periodical structure, determined by long spacing, was nearly the same in all the different types of fibres. A slight increase was observed after the treatment of viscose and modal fibres, but an unpronounced fall of a long period accompanied the pre-treatment of lyocell fibres. Some changes in crystallinity and crystalline orientation occurred due to the treatment conditions. The structural changes were correlated to the iodinesorption and mechanical properties.
Ključne besede: regenerated cellulose fibres, fibre structure, fibre properties, x-ray analysis, WAXS, SAXS, cellulose pre-treatment
Objavljeno: 01.06.2012; Ogledov: 876; Prenosov: 6
URL Polno besedilo (0,00 KB)

Functional materials from polysaccharides
Volker Ribitsch, Karin Stana-Kleinschek, 2013, objavljeni povzetek znanstvenega prispevka na konferenci (vabljeno predavanje)

Ključne besede: polisaharidi
Objavljeno: 10.07.2015; Ogledov: 440; Prenosov: 3
URL Polno besedilo (0,00 KB)

Preparation of water vapor barrier coatings employing a water based layer-by-layer approach
Gerald Findenig, Simon Leimgruber, Anna Dunkl, Volker Ribitsch, Rupert Kargl, Karin Stana-Kleinschek, 2013, objavljeni znanstveni prispevek na konferenci

Ključne besede: membrane
Objavljeno: 10.07.2015; Ogledov: 297; Prenosov: 0
URL Polno besedilo (0,00 KB)

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