A comparison between the morphology of semicrystalline polymer blends of poly(ε-caprolactone)/poly(vinyl methyl ether) and poly(ε-caprolactone)/(styrene-acrylonitrile)

The morphology of polymer blends of poly(ε-caprolactone) (PCL) and poly(vinyl methyl ether) (PVME) is compared with that of PCL and a random copolymer of styrene and acrylonitrile (SAN). The main objective is to determine the influence of the glass transition temperature of the amorphous component (Tg,a) on the morphology of the semicrystalline polymer blends. These blends represent the two extreme cases corresponding to Tc < Tg,a and Tc > Tg,a, where Tc is the crystallization temperature. The morphology of these blends, with PVME and SAN representing the amorphous components, have been studied by small angle X-ray scattering. For both blends the long period increases with the addition of amorphous polymer, which is a strong indication for an interlamellar morphology. D.s.c. experiments, including enthalpy relaxation, are used to investigate the crystallinity and the interphases. The overall amount of crystallinity in both blends decreases with increasing content of amorphous polymer. However, the fraction of PCL that crystallizes decreases in PCL/SAN and increases slightly in PCL/PVME. Apparently, the addition of the low Tg,a PVME improves the crystallization of PCL in accordance with a simple Gamblers Ruin Model type argument. The high Tg,a of SAN means this does not occur in PCL/SAN blends. Conventional d.s.c. experiments show an interphase of pure amorphous PCL in PCL/SAN blends and enthalpy relaxation experiments demonstrate its presence in PCL/PVME blends as well.

Enthalpy Relaxations and Concentration Fluctuations in Blends of Polystyrene and Poly(oxy-2,6-dimethyl-1,4-phenylene)

A series of enthalpy relaxation measurements were carried out for the pure polymers polystyrene (PS) and poly(oxy-2,6-dimethyl-1,4-phenylene) (PPE) and for homogeneous blends thereof. The data were analyzed using Moynihan's four-parameter approach. For the pure components the best fit parameter values for the simple cooling/heating experiments differ somewhat from those for the annealing experiments at least partly due to thermal lag. The amount of enthalpy relaxation during annealing of the blends turned out to be considerably lower than for the corresponding homopolymers. Moreover, the annealing experiments on the blends could not be fit satisfactorily with the Moynihan model. The first observation agrees with a similar result found by Cowie and Ferguson for blends of PS and poly(vinyl methyl ether). Since this effect is not present for a number of polymer blends involving polymers with comparable glass transition temperatures, it seems to be related to the large difference in glass transition temperatures of the blend components. The presence of concentration fluctuations, with a corresponding range of Tg values, is the most obvious explanation for both observations.

Random copolymer blends of styrene, para-fluoro styrene and ortho-fluoro styrene

This study completes the investigation of the phase behaviour of polymer blends involving styrene (S), ortho-fluoro styrene (oFS) and para-fluoro styrene (pFS). As before, due to the proximity of the glass transition temperatures of most blends investigated, the miscibility or immiscibility is established using the alternative thermal analysis method based on enthalpy recovery of samples annealed in the glassy state. In most respects the phase behaviour is similar to that of the corresponding chlorinated systems. The value of the Flory-Huggins parameter χS,oFS is much smaller than χS,pFS. However, the latter is approximately the same as χoFS,pFS and, as a consequence, a miscibility window as found in the system PS/P (oClS-co-pClS) is only present in PS/P(oFS-co-pFS) blends for rather low molecular weights.

GtfC Enzyme of Geobacillus sp. 12AMOR1 Represents a Novel Thermostable Type of GH70 4,6-α-Glucanotransferase That Synthesizes a Linear Alternating (α1 → 6)/(α1 → 4) α-Glucan and Delays Bread Staling

Starch-acting α-glucanotransferase enzymes are of great interest for applications in the food industry. In previous work, we have characterized various 4,6- and 4,3-α-glucanotransferases of the glycosyl hydrolase (GH) family 70 (subfamily GtfB), synthesizing linear or branched α-glucans. Thus far, GtfB enzymes have only been identified in mesophilic Lactobacilli. Database searches showed that related GtfC enzymes occur in Gram-positive bacteria of the genera Exiguobacterium, Bacillus, and Geobacillus, adapted to growth at more extreme temperatures. Here, we report characteristics of the Geobacillus sp. 12AMOR1 GtfC enzyme, with an optimal reaction temperature of 60 °C and a melting temperature of 68 °C, allowing starch conversions at relatively high temperatures. This thermostable 4,6-α-glucanotransferase has a novel product specificity, cleaving off predominantly maltose units from amylose, attaching them with an (α1 → 6)-linkage to acceptor substrates. In fact, this GtfC represents a novel maltogenic α-amylase. Detailed structural characterization of its starch-derived α-glucan products revealed that it yielded a unique polymer with alternating (α1 → 6)/(α1 → 4)-linked glucose units but without branches. Notably, this Geobacillus sp. 12AMOR1 GtfC enzyme showed clear antistaling effects in bread bakery products

The influence of amylose-LPC complex formation on the susceptibility of wheat starch to amylase

<p>This study was aimed to assess the role of lysophosphatidylcholine (LPC) in the development of slowly digestible starch (SOS). The influence of LPC, on the enzymatic degradation of diluted 9% wheat starch suspensions (w/w) was investigated, using an in vitro digestion method. Wheat starch suspensions containing 0.5-5% LPC (based on starch) were heated in a Rapid Visco Analyser (RVA) till 95 degrees C and subjected to enzyme hydrolysis by porcine pancreatic a-amylase at 37 degrees C for several digestion periods. In vitro digestion measurements demonstrated that complexing starch with 5% LPC leads to a 22% decrease in rate of reducing sugar compared to the reference while the samples containing 0.5% LPC showed an equal digestibility comparable to the control. A clear decrease in the formation of reducing sugars was observed in presence of 2-5% LPC, since the results after 15 min digestion imply the formation of SDS due to the formation of amylose-LPC inclusion complexes. The DSC measurements proved the presence of amylose-LPC inclusion complexes even after 240 min digestion demonstrating the low susceptibility of amylose-V complexes to amylase. (C) 2013 Elsevier Ltd. All rights reserved.</p>

Phenomenological theory of structural relaxation based on a thermorheologically complex relaxation time distribution

he aim of this work is to explore the consequences on the kinetics of structural relaxation of considering a glass-forming system to consist of a series of small but macroscopic relaxing regions that evolve independently from each other towards equilibrium in the glassy state. The result of this assumption is a thermorheologically complex model. In this approach each relaxing zone has been assumed to follow the Scherer-Hodge model for structural relaxation (with the small modification of taking a linear dependence of configurational heat capacity with temperature). The model thus developed contains four fitting parameters. A least-squares search routine has been used to find the set of model parameters that fit simultaneously four DSC thermograms in PVAc after different thermal histories. The computersimulated curves are compared with those obtained with Scherer-Hodge model and the model proposed by Gómez and Monleón. The evolution of the relaxation times during cooling or heating scans and also during isothermal annealing below the glass transition has been analysed. It has been shown that the relaxation times distribution narrows in the glassy state with respect to equilibrium. Isothermal annealing causes this distribution to broaden during the process to finally attain in equilibrium the shape defined at temperatures above T&lt;sub&gt;g&lt;/sub&gt;