Separation of quadrupolar and magnetic contributions to spin-lattice relaxation in the case of a single isotope

We present a NMR pulse double-irradiation method which allows one to separate magnetic from quadrupolar contributions in the spin–lattice relaxation. The pulse sequence fully saturates one transition while another is observed. In the presence of a Δm = 2 quadrupolar contribution, the intensity of the observed line is altered compared to a standard spin-echo experiment. We calculated analytically this intensity change for spins I = 1, , , thus providing a quantitative analysis of the experimental results. Since the pulse sequence we used takes care of the absorbed radiofrequency power, no problems due to heating arise. The method is especially suited when only one NMR sensitive isotope is available. Different cross-checks were performed to prove the reliability of the results obtained. The applicability of this method is demonstrated by a study of the plane oxygen ¹⁷O (I = ) in the high-temperature superconductor YBa₂Cu₄O₈: the ¹⁷O spin–lattice relaxation rate consists of magnetic as well as quadrupolar contributions.     

Thermal analysis,state transitions and food quality

Thermal properties of food systems are important in understanding relationships between food properties and changes in food quality. Concentrated food systems (low-moisture and frozen foods) are seldom in an equilibrium state and they tend to form amorphous, non-crystalline structures. Several glass transition-related changes in such foods affect stability, e.g., stickiness and caking of powders, crispness of snack foods and breakfast cereals, crystallisation of amorphous sugars, recrystallisation of gelatinised starch, ice formation and recrystallisation in frozen foods and rates of non-enzymatic browning and enzymatic reactions. Relationships between glass transition, water plasticisation and relaxation times can be shown in state diagrams. State diagrams are useful as stability or quality maps and in the control of rates of changes in food processing and storage.This revised version was published online in November 2005 with corrections to the Cover Date.     

Carboxymethyl cellulose on a fiber substrate: the interactions with cationic polyelectrolytes

High and low molecular weight (M_w) carboxymethyl celluloses (CMC) were adsorbed on a well-characterized fiber substrate (long fibers of a commercial bleached birch kraft pulp with the carboxylic acid groups in Na-form) to increase the charge of the fibers in a controlled fashion. The M_w played a role in the utilization of CMCs as a strength additive in paper sheets nearly doubling the tensile strength with the high M_w CMC. Swelling properties of the CMC treated fibers were measured with water retention value (WRV). The WRV increased more with the high M_w CMC. The swelling was further tuned by two highly cationic polyelectrolytes; high M_w poly(diallyldimethyl ammonium chloride) (PDADMAC) and low M_w polybrene (hexadimethrine bromide, [3,6]-ionene). They were chosen because of their known ability to neutralize the anionic charge either exclusively on the surface or in the whole fiber, respectively. Adsorption of PDADMAC could reduce WRV of the CMC pre-treated fibers to the level of the untreated reference, while polybrene adsorbed pulps with 3–10 times more cationic polyelectrolyte deswelled the fibers only slightly more than the surface neutralized fibers. These results indicated surface conformation differences with low and high M_w CMCs. While the conformation did play a role after physical alteration (drying and rewetting) of the fibers, the paper sheets produced from these fibers showed remarkable differences. In extreme cases, the strength of the paper could be retained after drying (low M_w CMC + PDADMAC) or paper, resistant to disintegration, could be achieved (CMC + polybrene).     

Thermoluminescence study of persistent luminescence materials: Eu2+- and R3+-doped calcium aluminates, CaAl2O4:Eu2+,R3+

Thermoluminescence properties of the Eu2+-, R3+-doped calcium aluminate materials, CaAl2O4:Eu2+,R3+, were studied above room temperature. The trap depths were estimated with the aid of the preheating and initial rise methods. The seemingly simple glow curve of CaAl2O4:Eu2+ peaking at ca. 80 degrees C was found to correspond to several traps. The Nd3+ and Tm3+ ions, which enhance most the intensity of the high-temperature TL peaks, form the most suitable traps for intense and long-lasting persistent luminescence, too. The location of the 4f and 5d ground levels of the R3+ and R2+ ions were deduced in relation to the band structure of CaAl2O4. No clear correlation was found between the trap depths and the R3+ or R2+ level locations. The traps may thus involve more complex mechanisms than the simple charge transfer to (or from) the R3+ ions. A new persistent luminescence mechanism presented is based on the photoionization of the electrons from Eu2+ to the conduction band followed by the electron trapping to an oxygen vacancy, which is aggregated with a calcium vacancy and a R3+ ion. The migration of the electron from one trap to another and also to the aggregated R3+ ion forming R2+ (or R3+-e-) is then occurring. The reverse process of a release of the electron from traps to Eu2+ will produce the persistent luminescence. The ability of the R3+ ions to trap electrons is probably based on the different reduction potentials and size of the R3+ ions. Hole trapping to a calcium vacancy and/or the R3+ ion may also occur. The mechanism presented can also explain why Na+, Sm3+, and Yb3+ suppress the persistent luminescence.     

Topochemical modification of cotton fibres with carboxymethyl cellulose

Adsorption of carboxymethyl cellulose (CMC) as a method to introduce charged (ionizable) groups onto cellulose cotton fibre surfaces was investigated. The method was based on application of a previously published method used for wood fibres. The amount of adsorbed ionizable groups was determined indirectly by analysis of CMC in solution by the phenol–sulphuric acid method and directly by conductometric titration of the fibres. Results from the two methods correlated well. The molecular weight and purity of the CMC had an influence on its adsorption onto cotton; high molecular weight CMC was preferentially adsorbed. The adsorbed charge correlated linearly with the amount of CMC adsorbed. The total charge of the cotton fibres could be increased by more than 50% by adsorption of CMC. It is expected that this modification procedure can be used in a wide spectrum of practical applications. Lidija Fras Zemljič and Karin Stana-Kleinschek are the members of the European Polysaccharide Network of Excellence (EPNOE).     

Wettability conversion on the liquid flame spray generated superhydrophobic TiO2 nanoparticle coating on paper and board by photocatalytic decomposition of spontaneously accumulated carbonaceous overlayer

Titanium dioxide (TiO₂) is a photoactive material with various interesting and useful properties. One of those is the perfect wettability of TiO₂ surface after ultraviolet (UV) illumination. Wettability of a solid surface plays an important role in the field of printing, coating, and adhesion among others. Here we report on a superhydrophobic and photoactive liquid flame spray (LFS) generated TiO₂ nanoparticle coating that can be applied on web-like materials such as paper and board in one-step roll-to-roll process. The LFS TiO₂ nanoparticle coated paper and board were superhydrophobic instantly after the coating procedure because of spontaneously accumulated carbonaceous overlayer on TiO₂, and thus there was no need for any type of separate hydrophobization treatment. The highly photoactive LFS TiO₂ nanoparticle coating could be converted steplessly from superhydrophobic to superhydrophilic by UV-illumination, and the coating gave strong response to natural daylight illumination even in the shade. The superhydrophobic LFS TiO₂ coated surface can be used as an intelligent substrate, where photo-generated hydrophilic patterns guide the fluid setting and figure formation. Our study reveals that the wettability changes on the LFS TiO₂ surface were primarily caused by the photocatalytic removal of the carbonaceous material from TiO₂ during the UV-illumination and spontaneous accumulation of the carbonaceous material on the surface of the metal oxide during storage in the dark. The latter mechanism was found to be a temperature activated process which could be significantly speeded up by heat treatment. If other mechanisms such as surface oxidization, increment of hydroxyl groups, or charge separation played a role in the wetting phenomena on TiO₂, their effect was rather secondary as the removal and accumulation of the carbonaceous material dominated the wettability changes on the surface. Our study gives valuable information on the complex issue of photo-induced wettability changes on TiO₂.     

Switchable water absorption of paper via liquid flame spray nanoparticle coating

Surface wetting/anti-wetting and liquid absorption are relevant properties of many porous solids including paper and other cellulose-based materials. Here we demonstrate how surface wetting by water and water absorption of commercially available kraft paper can be altered by thin nanoparticle coatings fabricated by liquid flame spray in facile and continuous one-step process. Surface wettability and absorption properties of paper increased with silica and decreased with titania (TiO₂) nanoparticle coatings. Moreover, the water-repellent (superhydrophobic) TiO₂ nanoparticle coated paper could be switched to superhydrophilic and water absorbing by ultraviolet illumination. The experiments revealed that although surface wetting and liquid absorption of nanoparticle coated paper are strongly related to each other, they are two distinct phenomena which do not necessarily correlate. We propose wetting regimes on the nanoparticle coated paper samples on the basis of the experimental observations.     

Formation of Octameric Methylaluminoxanes by Hydrolysis of Trimethylaluminum and the Mechanisms of Catalyst Activation in Single‐Site α‐Olefin Polymerization Catalysis

Hydrolysis of trimethylaluminum (TMA) leads to the formation of methylaluminoxanes (MAO) of general formula (MeAlO)_n(AlMe₃)_m. The thermodynamically favored pathway of MAO formation is followed up to n=8, showing the major impact of associated TMA on the structural characteristics of the MAOs. The MAOs bind up to five TMA molecules, thereby inducing transition from cages into rings and sheets. Zirconocene catalyst activation studies using model MAO co‐catalysts show the decisive role of the associated TMA in forming the catalytically active sites. Catalyst activation can take place either by Lewis‐acidic abstraction of an alkyl or halide ligand from the precatalyst or by reaction of the precatalyst with an MAO‐derived AlMe₂⁺ cation. Thermodynamics suggest that activation through AlMe₂⁺ transfer is the dominant mechanism because sites that are able to release AlMe₂⁺ are more abundant than Lewis‐acidic sites. The model catalyst system is demonstrated to polymerize ethene.     

Spatial distribution and decrease of dye solar cell performance induced by electrolyte filling

The spatial performance variation of dye solar cell with standard liquid electrolyte was examined by dividing the cell into segments. Surprisingly large and permanent performance differences were found in different parts of the cell leading to significant losses in the overall cell efficiency. The decrease of open circuit voltage along the electrolyte filling direction suggests that 4-tert-butylpyridine is adsorbed non-uniformly as the electrolyte passes through the dyed TiO₂ layer during the filling process. The result indicates that non-uniform electrolyte adsorption may limit the up-scaling of dye solar cells, which calls for the examination of electrolyte filling techniques and electrolyte compositions less prone to this effect.