Spin probe study of semi‐interpenetrating polymer networks based on polyurethane and polymethacrylate functional prepolymers

The motional transition and heterogeneity of semi‐interpenetrating networks (SIPNs) based on polyurethane (PU) with carboxylic groups and methacrylic copolymer (PM) with tertiary amine groups were studied by the electron spin resonance (ESR) spin probe method. The concentration of functional groups in both prepolymers varied from 0 to 0.45 mmol g^?1. Spin‐probed SIPNs show that the temperature‐dependent spectra are sensitive to polymer interactions imposed by functional groups. These interactions determine the free volume distribution in the matrix and temperature at which motional transition takes place. The fraction of free volume increases with functional group concentration and reaches its maximum at 0.25 mmol g^?1. Further increases in the functional group concentration reduce the free volume. The results of the networks with strong interactions are discussed in terms of the interference of the plasticizing effect of the PU component and the formation of possible cluster cross‐links, which restricts segmental motions. Copyright © 2003 Society of Chemical Industry     

Synthesis and characterization of phenolic and amino resins based on α, β-unsaturated aldehydes

Phenolic and amino resins on the basis of α,β-unsaturated aldehydes were synthesized in bulk or solution. Catalysts were HCl, H₃PO₄, or formic acid, and in some cases NaOH. The course of the reactions was followed by GPC and NMR while the structure of the reaction products was determined by one- and two-dimensional NMR. The course of the reactions is influenced by experimental conditions: the type of monomers, their molar ratio, the type and quantity of the catalyst, the reaction time and temperature, and the reaction medium. At the beginning of the reaction the addition of a nucleophile to an aldehyde takes place through parallel 1,2-addition to and 1,4-addition to group. Oligomers with ? OH, , and ? CHO functional groups are able to add new monomer units or to react mutually to form higher molecular weight addition and condensation products. The overall rate constants for the beginning of the reactions were between 10^?3 L/mol s for the high reactive mixtures and 10^?7 L/mol s for the less reactive mixtures. The resins were cured by heating at temperatures above 135°C with the addition of hexamethylenetetramine.     

Mass transfer in aerated fermentation broths in a stirred tank reactor

The volumetric mass transfer coefficients, k_La, measured in a pilot plant (0.1 m³) and an industrial (67.5 m³) fermentor during an actual fermentation process are presented. Problems related to the estimation of the phsyical properties as well as to the correlation of experimental data and to scale up procedures are discussed. Although the scale up factor was rather high, both sets of data could be represented by single correlation. Comparison of the experimental data with several available correlations demonstrated the need for pilot plant experiments and scale up procedures, since it is almost impossible to take into account all relevant system properties.     

Determination of 200 °C Isothermal Section of Al-Ag-Ga Phase Diagram by Microanalysis,X-ray Diffraction,Hardness and Electrical Conductivity Measurements

Ternary Al-Ag-Ga system at 200 °C was experimentally and thermodynamically assessed. Isothermal section was extrapolated using optimized thermodynamic parameters for constitutive binary systems. Microstructure and phase composition of the selected alloy samples were analyzed using light microscopy, scanning electron microscopy combined with energy-dispersive spectrometry and x-ray powder diffraction technique. The obtained experimental results were found to be in a close agreement with the predicted phase equilibria. Hardness and electrical conductivity of the alloy samples from four vertical sections Al-Ag₈₀Ga₂₀, Al-Ag₆₀Ga₄₀, Ag-Al₈₀Ga₂₀ and Ag-Al₆₀Ga₄₀ of the ternary Al-Ag-Ga system at 200 °C were experimentally determined using Brinell method and eddy current measurements. Additionally, hardness of the individual phases present in the microstructure of the studied alloy samples was determined using Vickers microhardness test. Based on experimentally obtained results, isolines of Brinell hardness and electrical conductivity were calculated for the alloys from isothermal section of the ternary Al-Ag-Ga system at 200 °C.     

Water Sorption and Diffusion in (Reduced) Graphene Oxide‐Alginate Biopolymer Nanocomposites

The water sorption and diffusion in (reduced) graphene oxide‐alginate composites of various compositions is analyzed. Water sorption of sodium alginate can be significantly reduced by the inclusion of graphene oxide sheets due to the formation of an extensive hydrogen bonding network between oxygenated groups. Crosslinking alginate with divalent metal ions and the presence of reduced graphene oxide can further improve the swelling resistance due to the strong interactions between metal ions, alginate, and filler sheets. Depending on conditions and composition, the overall water barrier properties of alginate composites improve upon (reduced) graphene oxide filling, making them attractive for moisture barrier coating applications. Water sorption kinetics in all alginate composites indicate a non‐Fickian diffusion process that can be accurately described by the Variable Surface Concentration model. In addition, the water barrier properties of sodium alginate‐graphene oxide composites can be adequately predicted using a simple model that takes the orientational order of filler sheets and their effective aspect ratio into account.

     

Ionic polymers with tunable liquid‐crystalline properties

Side‐chain polyesters were synthesized from N‐octyl‐, N‐dodecyl‐ or N‐hexadecyl‐diethanolamine and succinic acid anhydride. These polyesters were then transformed into polyester hydrochlorides by protonation of the amino groups using different amounts of HCl (20–100 mol%). Above 60 mol% the reaction is not quantitative and a degree of protonation of up to 88% is obtained. The structures of the synthesized polyesters and their hydrochlorides were determined by ¹H nuclear magnetic resonance spectroscopy. The thermal properties of the synthesized polyesters and their hydrochlorides were also studied using differential scanning calorimetry in relation to the side‐chain length and the degree of polyester protonation. The polyester with octyl side chains and its hydrochlorides were amorphous liquids at room temperature, while the polyester and polyester hydrochlorides with hexadecyl side chains formed a smectic crystalline phase, S_mB, or its tilted analogues. The polyester with a dodecyl side chain was also an amorphous liquid at room temperature, while its hydrochlorides with various degrees of protonation were smectic liquid crystals, as determined by X‐ray diffraction. By simply varying the degree of protonation the liquid crystal isotropization temperature was increased from 32 °C to 82 °C. Copyright © 2011 Society of Chemical Industry     

An experimental test of Occam’s razor in classification

A widely persisting interpretation of Occam’s razor is that given two classifiers with the same training error, the simpler classifier is more likely to generalize better. Within a long-lasting debate in the machine learning community over Occam’s razor, Domingos (Data Min. Knowl. Discov. 3:409–425, 1999) rejects this interpretation and proposes that model complexity is only a confounding factor usually correlated with the number of models from which the learner selects. It is thus hypothesized that the risk of overfitting (poor generalization) follows only from the number of model tests rather than the complexity of the selected model. We test this hypothesis on 30 UCI data sets using polynomial classification models. The results confirm Domingos’ hypothesis on the 0.05 significance level and thus refutes the above interpretation of Occam’s razor. Our experiments however also illustrate that decoupling the two factors (model complexity and number of model tests) is problematic.     

Step-growth polymerization of guanamines with unsaturated aldehydes

Summary In acid medium and at temperatures from 50 to 100°C the resins from three different guanamines and three different unsaturated aldehydes were synthesized. The products were red coloured resins, which were soluble in organic solvents and were able to cure with hexamethylenetetramine to form hard and almost insoluble products. Using a combination of NMR and GPC methods it was possible to predict the course and the mechanism of the reactions. The rates of the reactions depend on the reaction conditions and on the type of the monomer.