Physical crosslinking effects in α,ω-dihydroxy terminated polybutadienes

Structure and molecular dynamics of α,ω-dihydroxy terminated polybutadienes of varying number averaged molecular weight (1320-10?500 g/mol) have been investigated by Fourier-transformed infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, dielectric relaxation spectroscopy (DRS), differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS). DSC and DRS revealed an increase in the glass transition temperature upon decrease of the molecular weight, accompanied by an increasing dynamic fragility m (or steepness index) of the dielectric α-process. This correlation between T_g and m for different molecular weights indicates the presence of a physical network, where H-bonded end-group clusters act as temporary crosslinks. From the dielectric relaxation strength Δ?_α(M_n), the fraction of associated hydroxy groups (f_bond) was estimated showing a peak value for the two but shortest polymers, a behaviour that strongly resembles the molecular weight dependence of the fragility. By considering the quantity f_bond(M_n) in a modified Fox-Flory approach, the measured T_g(M_n) behaviour could be reproduced in a satisfying way. FTIR results support this general picture and show a considerable dependence of the extent of hydrogen bonding and formation of hydroxy groups associates on the molecular weight. Further, WAXS and DSC results disprove the idea of formation of pseudo-crystalline hydrophobic microdomains in these compounds as suggested by other authors.     

Continuous Levels‐of‐Detail and Visual Abstraction for Seamless Molecular Visualization

Molecular visualization is often challenged with rendering of large molecular structures in real time. We introduce a novel approach that enables us to show even large protein complexes. Our method is based on the level‐of‐detail concept, where we exploit three different abstractions combined in one visualization. Firstly, molecular surface abstraction exploits three different surfaces, solvent‐excluded surface (SES), Gaussian kernels and van der Waals spheres, combined as one surface by linear interpolation. Secondly, we introduce three shading abstraction levels and a method for creating seamless transitions between these representations. The SES representation with full shading and added contours stands in focus while on the other side a sphere representation of a cluster of atoms with constant shading and without contours provide the context. Thirdly, we propose a hierarchical abstraction based on a set of clusters formed on molecular atoms. All three abstraction models are driven by one importance function classifying the scene into the near‐, mid‐ and far‐field. Moreover, we introduce a methodology to render the entire molecule directly using the A‐buffer technique, which further improves the performance. The rendering performance is evaluated on series of molecules of varying atom counts.     

Approximate Symmetry Detection in Partial 3D Meshes

Symmetry is a common characteristic in natural and man‐made objects. Its ubiquitous nature can be exploited to facilitate the analysis and processing of computational representations of real objects. In particular, in computer graphics, the detection of symmetries in 3D geometry has enabled a number of applications in modeling and reconstruction. However, the problem of symmetry detection in incomplete geometry remains a challenging task. In this paper, we propose a vote‐based approach to detect symmetry in 3D shapes, with special interest in models with large missing parts. Our algorithm generates a set of candidate symmetries by matching local maxima of a surface function based on the heat diffusion in local domains, which guarantee robustness to missing data. In order to deal with local perturbations, we propose a multi‐scale surface function that is useful to select a set of distinctive points over which the approximate symmetries are defined. In addition, we introduce a vote‐based scheme that is aware of the partiality, and therefore reduces the number of false positive votes for the candidate symmetries. We show the effectiveness of our method in a varied set of 3D shapes and different levels of partiality. Furthermore, we show the applicability of our algorithm in the repair and completion of challenging reassembled objects in the context of cultural heritage.     

Filters of implication reducts of basic algebras

Since basic algebras were introduced as a common generalization of MV-algebras and orthomodular lattices, their implication reducts form a common generalization of BCK-algebras and orthoimplication algebras introduced by J. C. Abbott. As shown in our previous paper, congruences in these implication reducts are in a one-to-one correspondence with their kernels. Hence, to characterize congruences it is enough to describe its kernels which is done in the paper.     

Photocatalytic degradation rate of oxalic acid on the semiconductive layer of n-TiO2 particles in the batch mode plate reactor Part I: Mass transfer limits

Organic compounds dissolved in water can be decomposed on a layer of n-TiO2 particles irradiated by u.v. light, which generates holes and electrons in the TiO2 material. Dissolved oxygen was used as electron scavenger and holes reacted with water to give OH radicals. The rate of degradation of the dissolved organic compounds by OH radicals is limited by the transfer of either oxygen or of theorganic compounds to the surface of n-TiO2 particles. The consequence of these limits is that, in the batch mode reactor with recirculation of the liquid, the dependence of the concentration of an organic compound on time has either a linear or an exponential form. Experiments with decomposition of oxalic acid in aqueous solutions using a plate reactor (60 cm × 120 cm) confirmed the analysis. Equations for evaluation of the mass transfer coefficient of the dissolved species to the surface of the plate reactor with a moving liquid fil m were developed for the case of the thickness of the Nernst diffusion layer being thinner than the thickness of the liquid. The experimentally obtained decomposition rate of oxalic acid was about 60 to 80% of the theoretical decomposition rate limited by oxygen flux through the film of a moving liquid. The present theory neglects the diffusion of oxygen into the porous layer of n-TiO2.     

Influence of anionic form on thermooxidation of TMAHP–cellulose

With the help of DTA, DTG elementary analysis of carbonized residues and ESR spectroscopy the influence of anionic form on thermooxidation of trimethylammoniumhydroxyprophyl (TMAHP)–cellulose was studied. At 300°C the percentage of carbon in carbonized residue thermolyzed in oxidative atmosphere is higher than for the sample degraded in inert atmosphere. The percentage of hydrogen decreases simultaneously. The concentration of free radicals in thermolyzed residue also increases due to the presence of oxygen. We propose that oxygen is abstracting the hydrogen atoms from polysaccharide and unpaired electrons on carbon atoms are produced. At 400°C the percentage of carbon in residues prepared at inert atmosphere is higher than for residue formed at oxidative atmosphere. Also the concentration of free radicals in thermolyzed residues obtained in inert atmosphere is greater than for those from oxidative ones. That is why suppose that at this temperature oxygen is bonded to polysaccharide residue and free radicals are terminated. From the semiquantitative DTA we can make the following sequence of samples according to their increasing thermooxidative effect: unmodified cellulose < A–HSO < A–Br^? < A–I^? < A–NO < A–H₂PO < A–CH₃COO^? < A–HCO < A–F^? < A–Cl^?1 < A–OH^p?.     

The potentiometric behaviour of copolymers of methacrylic acid in water-ethanol solutions

Summary The synthesis is reported of copolymers of styrene with methacrylic acid and of methyl methacrylate with methacrylic acid by radical copolymerization, of copolymers of methyl methacrylate with methacrylic acid by partial alkaline hydrolysis of poly(methyl methacrylate), and of block copolymers of styrene with methacrylic acid. Modified titration curves of all these copolymers were recorded in water and water-ethanol solutions. In a solution containing 50 mass.% ethanol, only small differences could be observed between the potentiometric behaviour of the individual copolymers and polymethacrylic acid. Also, there were no essential differences in any of the solvents used between the potentiometric behaviour of block copolymers of styrene with methacrylic acid, on the one hand, and polymethacrylic acid, on the other. On the contrary, maxima and minima were always observed on the modified titration curves of statistical copolymers with a higher content of the hydrophobic comonomer in solutions with a high water content. Thus, using the modified titration curves, it is possible to decide whether a given copolymer is of the block or statistical type.     

Investigation of Flow Patterns in Continuous‐flow Stirred Vessels by Laser Doppler Velocimetry

The flow structure of a continuous‐flow reactor stirred by a Rushton turbine was investigated by laser Doppler velocimetry for two different mean residence time‐mixing time ratios. Velocity measurements were obtained for two inlet locations, corresponding to the incoming liquid stream being fed co‐currently or counter‐currently to the flow discharged by the turbine. In all investigated configurations and for all operating conditions, it was found that the flow disruption caused by the incoming liquid stream was observable mainly in the first vessel quarter, which followed the feed‐tube plane. From comparison of the velocities encountered in the various planes in the continuous‐flow reactor to the velocities of the batch reactor, it was also concluded that it may be possible to intensify the usage of the turbine‐stirred vessel by decreasing the characteristic times ratio, without considerable flow by‐pass and/or short‐circuiting problems.     

Diffusion of ellipsoidal granular particles in shear flow

The diffusion of nonspherical particles has not been well understood due to the complexity of their contact mechanics and self-organization of their orientations. We perform discrete element method simulations of monodisperse ellipsoids in a shear flow with Lees-Edwards boundary conditions to quantify the relation between the diffusion coefficient and the flow parameters. The results indicate that the particle aspect ratio strongly affects the diffusion coefficient by influencing the particle orientation and alignment. We develop a scaling law for the diffusion coefficient perpendicular to the flow direction, D_yy, which combines the influences of the shear rate , the solids fraction f, the effective particle diameter d_eff and the particle aspect ratio Z. We show that , where k_d is a dimensionless pre-factor, and a fit is obtained for the functional form of χ(f, Z). This scaling law will be useful in developing continuum transport models for applications.     

Mid‐infrared spectroscopy as a tool for real‐time monitoring of ethanol absorption in glycols

Fast, simple, accurate, and inexpensive methods for obtaining analyte concentration data are desirable in the industrial sector. In the present study, the use of Fourier transform mid‐infrared (FT‐MIR) spectroscopy, combined with partial least squares (PLS) regression, was investigated as a tool for real‐time monitoring of processes of ethanol absorption in glycols. Calibration was performed using simple synthetic samples containing ethanol, water, and monoethylene glycol (MEG) or diethylene glycol (DEG). The PLS models presented excellent performance, with correlation coefficients (R²) close to unity and root‐mean‐square errors of cross‐validation (RMSECV) and prediction (RMSEP) lower than 2% of the calibration data ranges for both analytes (ethanol and water) in both absorbents (MEG and DEG). The monitoring technique developed has potential to be applied in absorption processes and could also be used in other large‐scale unit operations, providing information in real time and enhancing process control.