Characterisation of amorphous and nanocrystalline molecular materials by total scattering

The use of high-energy X-ray total scattering coupled with pair distribution function analysis produces unique structural fingerprints from amorphous and nanostructured phases of the pharmaceuticals carbamazepine and indomethacin. The advantages of such facility-based experiments over laboratory-based ones are discussed and the technique is illustrated with the characterisation of a melt-quenched sample of carbamazepine as a nanocrystalline (4.5 nm domain diameter) version of form III.

The radiative effect of a fir canopy on a snowpack

Models of snow processes in areas of possible large-scale change need to be site independent and physically based. Here, the accumulation and ablation of the seasonal snow cover beneath a fir canopy has been simulated with a new physically based snow-soil vegetation-atmosphere transfer scheme (Snow-SVAT) called SNOWCAN. The model was formulated by coupling a canopy optical and thermal radiation model to a physically based multilayer snow model. Simple representations of other forest effects were included. These include the reduction of wind speed and hence turbulent transfer beneath the canopy, sublimation of intercepted snow, and deposition of debris on the surface. This paper tests this new modeling approach fully at a fir site within Reynolds Creek Experimental Watershed, Idaho. Model parameters were determined at an open site and subsequently applied to the fir site. SNOWCAN was evaluated using measurements of snow depth, subcanopy solar and thermal radiation, and snowpack profiles of temperature, density, and grain size. Simulations showed good agreement with observations (e.g., fir site snow depth was estimated over the season with r(2) = 0.96), generally to within measurement error. However, the simulated temperature profiles were less accurate after a melt-freeze event, when the temperature discrepancy resulted from underestimation of the rate of liquid water flow and/or the rate of refreeze. This indicates both that the general modeling approach is applicable and that a still more complete representation of liquid water in the snowpack will be important.

The structure of crystallisable copolymers of L-lactide, epsilon-caprolactone and glycolide

We apply a new X-ray scattering approach to the study of melt-spun filaments of tri-block and random terpolymers prepared from lactide, caprolactone and glycolide. Both terpolymers contain random sequences, in both cases the overall fraction of lactide units is similar to 0.7 and C-13 and H-1 NMR shows the lactide sequence length to be similar to 9-10. A novel representation of the X-ray fibre pattern as series of spherical harmonic functions considerably facilitates the comparison of the scattering from the minority crystalline phase with hot drawn fibres prepared from the poly(L-lactide) homopolymer. Although the fibres exhibit rather disordered structures we show that the crystal structure is equivalent to that displayed by poly(L-lactide) for both the block and random terpolymers. There are variations in the development of a two-phase structure which reflect the differences in the chain architectures. There is evidence that the random terpolymer includes non-lactide units in to the crystal interfaces to achieve a well defined two-phase structure. (c) 2005 Published by Elsevier Ltd.

A novel approach to processing high-performance polymers that exploits entropically driven ring-opening polymerization

Blends of the poly(ether sulfone) derived from 4,4'-biphenol and 4,4'-dichlorodiphenylsulfone (Radel-R(TM)) with its homologous macrocyclic oligomers show greatly lowered melt viscosities relative to that of the parent polymer, potentially enabling more facile production and fabrication of fiber-reinforced composite materials. The macrocycles can then undergo entropically driven ring-opening polymerization in situ. The required blends can be obtained easily in one step, by carrying out polycondensations at concentrations lower than those usually used for polymer synthesis.

Fractionated crystallization and fractionated melting of confined PEO microdomains in PB-b-PEO and PE-b-PEO diblock copolymers

The confined crystallization of poly(ethylene oxide) (PEO) in predominantly spherical microdomains formed by several diblock copolymers was studied and compared. Two polybutadiene-b-poly(ethylene oxide) diblock copolymers were prepared by sequential anionic polymerization (with approximately 90 and 80 wt % polybutadiene (PB)). These were compared to equivalent samples after catalytic hydrogenation that produced double crystalline polyethylene-b-poly(ethylene oxide) diblock copolymers. Both systems are segregated into microdomains as indicated by small-angle X-ray scattering (SAXS) experiments performed in the melt and at lower temperatures. However, the PB-b-PEO systems exhibited a higher degree of order in the melt. A predominantly spherical morphology of PEO in a PB or a PE matrix was observed by both SAXS and transmission electron microscopy, although a possibly mixed morphology (spheres and cylinders) was formed when the PEO composition was close to the cylinder-sphere domain transitional composition as indicated by SAXS. Differential scanning calorimetry experiments showed that a fractionated crystallization process for the PEO occurred in all samples, indicating that the PE cannot nucleate PEO in these diblock copolymers. A novel result was the observation of a subsequent fractionated melting that reflected the crystallization process. Sequential isothermal crystallization experiments allowed us to thermally separate at least three different crystallization and melting peaks for the PEO microdomains. The lowest melting point fraction was the most important in terms of quantity and corresponded to the crystallization of isolated PEO spheres (or cylinders) that were either superficially or homogeneously nucleated. This was confirmed by Avrami index values of approximately 1. The isothermal crystallization results indicate that the PE matrix restricts the crystallization of the covalently bonded PEO to a higher degree compared to PB.

Crystal and molecular structure of the thioether-analogue of PEEK from X-ray powder data and diffraction-modelling

Analysis of X-ray powder data for the melt-crystallisable aromatic poly(thioether thioether ketone) [-S-Ar-S-Ar-CO-Ar](n), ('PTTK', Ar= 1,4-phenylene), reveals that it adopts a crystal structure very different from that established for its ether-analogue PEEK. Molecular modelling and diffraction-simulation studies of PTTK show that the structure of this polymer is analogous to that of melt-crystallised poly(thioetherketone) [-SAr-CO-Ar](n) in which the carbonyl linkages in symmetry-related chains are aligned anti-parallel to one another. and that these bridging units are crystallographically interchangeable. The final model for the crystal structure of PTTK is thus disordered, in the monoclinic space group 121a (two chains per unit cell), with cell dimensions a = 7.83, b = 6.06, c = 10.35 angstrom, beta = 93.47 degrees. (c) 2005 Elsevier Ltd. All rights reserved.

Enthalpy-driven ring-opening polymerization of highly strained macrocyclic biaryl-ether-ketones

Highly strained macrocyclic ether-ketones obtained by nickel-catalyzed cyclization of linear precursor oligomers undergo ring-opening polyinerization via ether exchange in the presence of nucleophilic initiators such as fluoride or phenoxide anions. Strain enthapies of these macrocycles, from DSC analyses of their exothermic ring-opening polymerization are in the range 50-90 kJ mol(-1). Melt-phase polymerization generally affords slightly cross-linked materials, but solution-phase polymerization at high macrocycle concentrations gives fully soluble, high molar mass polymers with inherent viscosities of up to 1.78 dL g(-1). Sequence-analysis of the resulting polymers by C-13 NMR shows that alternating or random monomer sequences may be obtained, depending on whether one or both aromatic rings adjacent to the ether linkages are activated toward nucleophilic attack.

Microfabrication of high-performance aromatic polymers as nanotubes or fibrils by in situ ring-opening polymerisation of macrocyclic precursors

Melt-phase nucleophilic ring-opening polymerisation of macrocyclic aromatic ethers and thioethers at high temperatures within the cylindrical pores of an anodic-alumina membrane, followed by dissolution of the template, enables replication of the membrane's internal pore structure and so affords high-performance aromatic polymers with well-defined fibrillar or tubular morphologies.

SAXS observation of RCM1 under cyclical shear

A cylinder forming poly(styrene-b-butadiene-b-styrene) triblock copolymer melt is cyclically processed through a capillary at a high shear rate in the Cambridge Multipass Rheometer (MPR). In situ X-ray diffraction experiments enable observation of the effect of the shear on the block copolymer (BCP) nanophase orientation, both during and after processing. Temporal resolution of the X-ray exposures is increased, whilst retaining intensity, by exploiting the cyclical nature of the shear and the material's response to it; short exposures from many cycles, individually having few counts, are added together to produce well resolved X-ray patterns. Orientation of the cylinders reduces during processing, then increases during pauses between processing. The loss of orientation is attributed to the high shear rate deforming the melt faster than the structure can respond, whilst it is believed that melt relaxation, linked to the compressibility of the material, produces much lower shear rates after mechanical processing has ceased, which induces strong orientation of the nanostructure.

Crystallization in poly(L-lactide)-b-poly(epsilon-caprolactone) double crystalline diblock copolymers: a study using X-ray scattering, differential scanning calorimetry, and polarized optical microscopy

The crystallization of well-defined poly(L-lactide)-b-poly(epsilon-caprolactone) diblock copolymers, PLLA-b-PCL, was investigated by time-resolved X-ray techniques, polarized optical microscopy (POM), and differential scanning calorimetry (DSC). Two compositions were studied that contained 44 and 60 wt % poly(L-lactide), PLLA (they are referred to as (L44C5614)-C-11 and (L60C409)-C-12, respectively, with the molecular weight of each block in kg/mol as superscript). The copolymers were found to be initially miscible in the melt according to small-angle X-ray scattering measurements (SAXS). Their thermal behavior was also indicative of samples whose crystallization proceeds from a mixed melt. Sequential isothermal crystallization from the melt at 100 degreesC (for 30 min) and then at 30 degreesC (for 15 min) was measured. At 100 degreesC only the PLLA block is capable of crystallization, and its crystallization kinetics was followed by both WAXS and DSC; comparable results were obtained that indicated an instantaneous nucleation with three-dimensional superstructures (Avrami index of approximately 3). The spherulitic nature of the superstructure was confirmed by POM. When the temperature was decreased to 30 degreesC, the PCL block was able to crystallize within the PLLA negative spherulites (with an Avrami index of 2, as opposed to 3 in homo-PCL), and its crystallization rate was much slower than an equivalent homo-PCL. Time-resolved SAXS experiments in (L60C409)-C-12 revealed an initial melt mixed morphology at 165 degreesC that upon cooling transformed into a transient microphase-separated lamellar structure prior to crystallization at 100 degreesC.

The effect of PEG crystallization on the morphology of PEG/peptide block copolymers containing amyloid beta-peptide fragments

Ordered nanostructures are observed in the melt and solid state for a series of three peptide/PEG conjugates containing fragments of amyloid beta-peptides. These are conjugated to PEG with (M) over bar (n) = 3 300 g.mol(-1) and a melting temperature T-m = 45-50 degrees C. The morphology at room temperature is examined by AFM and POM. This shows spherulite formation for the weakly fibrillizing KLVFF-PEG sample but fibril formation for FFKLVFF-PEG. The fibrillization tendency of the latter is enhanced by multiple phenylalanine residues. Simultaneous SAXS and WAXS was used to investigate the morphology as a function of temperature. The secondary structure is probed by FTIR.

Effect of sequence distribution on the morphology, crystallization, melting, and biodegradation of poly(epsilon-caprolactone-co-epsilon-caprolactam) copolymers

Two types of poly(epsilon-caprolactone (CLo)-co-poly(epsilon-caprolactam (CLa)) copolymers were prepared by catalyzed hydrolytic ring-opening polymerization. Both cyclic comonomers were added simultaneously in the reaction medium for the First type or materials where copolymers have a random distribution of counits, as evidenced by H-1 and C-13 NMR. For the second type of copolymers, the cyclic comonomers were added sequentially, yielding diblock poly(ester-amides). The materials were characterized by differential scanning calorimetry (DSC), wide- and small-angle X-ray scattering (WAXS and SAXS), and transmission and scanning electron microscopies (TEM and SEM). Their biodegradation in compost was also studied. All copolymers were found to be miscible by the absence of structure in the melt. TEM revealed that all samples exhibited a crystalline lamellar morphology. DSC and WAXS showed that in a wide composition range (CLo contents from 6 to 55%) only the CLa units were capable of crystallization in the random copolymers. The block copolymer samples only experience a small reduction of crystallization and melting temperature with composition, and this was attributed to a dilution effect caused by the miscible noncrystalline CLo units. The comparison between block and random copolymers provided a unique opportunity to distinguish the dilution effect of the CLo units on the crystallization and melting of the polyamide phase from the chemical composition effect in the random copolymers case, where the CLa sequences are interrupted statistically by the CLo units, making the crystallization of the polyamide strongly composition dependent. Finally, the enzymatic degradation of the copolymers in composted soil indicate a synergistic behavior where much faster degradation was obtained for random copolymers witha CLo content larger than 30% than for neat PCL.

Thermal Fractionation and isothermal crystallization of polyethylene nanocomposites prepared by in situ polymerization

Nanocomposites of high-density polyethylene (HDPE) and carbon nanotubes (CNT) of different geometries (single wall, double wall, and multiwall; SWNT, DWNT, and MWNT) were prepared by in situ polymerization of ethylene on CNT whose surface had been previously treated with a metallocene catalytic system. In this work, we have studied the effects of applying the successive self-nucleation and annealing thermal fractionation technique (SSA) to the nanocomposites and have also determined the influence of composition and type of CNT on the isothermal crystallization behavior of the HDPE. SSA results indicate that all types of CNT induce the formation of a population of thicker lamellar crystals that melt at higher temperatures as compared to the crystals formed in neat HDPE prepared under the same catalytic and polymerization conditions and subjected to the same SSA treatment. Furthermore, the peculiar morphology induced by the CNT on the HDPE matrix allows the resolution of thermal fractionation to be much better. The isothermal crystallization results indicated that the strong nucleation effect caused by CNT reduced the supercooling needed for crystallization. The interaction between the HDPE chains and the surface of the CNT is probably very strong as judged by the results obtained, even though it is only physical in nature. When the total crystallinity achieved during isothermal crystallization is considered as a function of CNT content, it was found that a competition between nucleation and topological confinement could account for the results. At low CNT content the crystallinity increases (because of the nucleating effect of CNT on HDPE), however, at higher CNT content there is a dramatic reduction in crystallinity reflecting the increased confinement experienced by the HDPE chains at the interfaces which are extremely large in these nanocomposites. Another consequence of these strong interactions is the remarkable decrease in Avrami index as CNT content increases. When the Avrami index reduces to I or lower, nucleation dominates the overall kinetics as a consequence of confinement effects. Wide-angle X-ray experiments were performed at a high-energy synchrotron source and demonstrated that no change in the orthorhombic unit cell of HDPE occurred during crystallization with or without CNT.

Bubble-included chocolate: relating structure with sensory response

Bubbles impart a very unique texture, chew, and mouth feel to foods. However, little is known about the relationship between structure of such products and consumer response in terms of mouth-feel and eating experience. The objective of this article is to investigate the sensory properties of 4 types of bubble-containing chocolates, produced by using different gases: carbon dioxide, nitrogen, nitrous oxide, and argon. The structure of these chocolates were characterized in terms of (1) gas hold-up values determined by density measurements and (2) bubble size distribution which was measured by undertaking an image analysis of X-ray microtomograph sections. Bubble size distributions were obtained by measuring bubble volumes after reconstructing 3D images from the tomographic sections. A sensory study was undertaken by a nonexpert panel of 20 panelists and their responses were analyzed using qualitative descriptive analysis (QDA). The results show that chocolates made from the 4 gases could be divided into 2 groups on the basis of bubble volume and gas hold-up: the samples produced using carbon dioxide and nitrous oxide had a distinctly higher gas hold-up containing larger bubbles in comparison with those produced using argon and nitrogen. The sensory study also demonstrated that chocolates made with the latter were perceived to be harder, less aerated, slow to melt in the mouth, and having overall flavor intensity. These products were further found to be creamier than the chocolates made by using carbon dioxide and nitrous oxide; the latter sample also showed a higher intensity of cocoa flavor.

Morphologies of block copolymer melts

Morphology formation by block copolymers in the melt is reviewed, considering both theoretical and experimental aspects. Comprehensive tables provide information on morphology identification for many block copolymer systems. A particular focus is on recent structural studies on ABC triblocks and rod–coil copolymers.