Characterization of the layered structure in main chain dibenzo-18-crown-6 ether polymers by simultaneous WAXS/MAXS-SAXS/DSC measurements

The structure and thermal properties of polymers containing dibenzo-18-crown-6 ether units in the main chain linked to an aliphatic spacer of different lengths (C10-C14) is reported. X-ray diffraction patterns of all the studied samples exhibit a peak in the medium angle region, revealing the existence of a lamellar structure. Simultaneous calorimetry and small, medium (SAXS-MAXS) and wide (WAXS) X-ray measurements during cooling and subsequent heating of the samples reveal that a layer phase is formed upon cooling. In the case of the homopolymers, this phase is almost simultaneously accompanied by the appearance of some reflections in the wide angle region as an indication of lateral crystallization. However, by copolymerization, the formation of the layer phase is decoupled from lateral crystallization, being stable in a wide temperature region.

WAXS studies of global molecular orientation induced in nematic liquid crystals by simple shear flow

Global molecular orientation function coefficients for the nematic liquid crystal 4-cyano 4'-nn -pentylbiphenyl (5CB) in shear flow are presented, being extracted from 2-dimensional Wide-Angle X-ray Scattering data. A linear increase in orientation parameter P2 is observed with a logarithmic increase in shear rate. It is proposed that this arises from an increased number of LC directors aligning to the shear axis. Upon cessation of shear flow, the anisotropy is seen to relax away completely, over a time scale which is inversely proportional to the previously applied shear rate.

The development of organized structures in polyethylene crystallized from a sheared melt, analyzed by WAXS and TEM

The development of global orientation and morphological features in linear polyethylene crystallizing from a sheared melt are studied using in-situ time-resolving wide angle X-ray scattering (WAXS) and ex-situ transmission electron microscopy. It is found that samples subjected to a shear rate above a critical value of ~1s-1 result in macroscopically oriented structures in the crystallized sample. This critical shear rate appears to be independent of the differences in molecular weight distribution of the samples studied although the morphologies which develop are sensitive to quite small differences in molecular weight distributions. The presence of shish kebabs in the morphology is shown to differ markedly according to variations in the upper molecular weight fraction of the molecular weight distribution, even though the resulting global orientation does not. The WAXS also reveals that areas which evidence no row nucleated structures still realize high degrees of molecular orientation. It is proposed that the formation of shish kebab or lamellar morphologies in these samples is dependent on the critical density of contiguous elongated crystallization nuclei rather than any specific global criteria.

XAS/WAXS time-resolved phase speciation of chlorine LDH thermal transformation: Emerging roles of isovalent metal substitution

The XAS/WAXS time-resolved method was applied for unraveling the complex mechanisms arising from the evolution of several metastable intermediates during the degradation of chlorine layered double hydroxide (LDH) upon heating to 450 °C, i.e., Zn2Al(OH)6·nH2O, ZnCuAl(OH)6·nH2O, Zn2Al 0.75Fe0.25(OH)6·nH2O, and ZnCuAl0.5Fe0.5(OH)6·nH2O. After a contraction of the interlamellar distance, attributed to the loss of intracrystalline water molecules, this distance experiences an expansion (T > 175-225 °C) before the breakdown of the lamellar framework around 275-295 °C. Amorphous prenucleus clusters with crystallo-chemical local order of zinc-based oxide and zinc-based spinel phases, and if any of copper-based oxide, are formed at T > 175-225 °C well before the loss of stacking of LDH layers. This distance expansion has been ascribed to the migration of Zn II from octahedral layers to tetrahedral sites in the interlayer space, nucleating the nano-ZnO or nano-ZnM2O4 (M = Al or Fe) amorphous prenuclei. The transformation of these nano-ZnO clusters toward ZnO crystallites proceeds through an agglomeration process occurring before the complete loss of layer stacking for Zn2Al(OH)6· nH2O and Zn2Al0.75Fe0.25(OH) 6·nH2O. For ZnCuAl(OH)6·nH 2O and ZnCuAl0.5Fe0.5(OH)6· nH2O, a cooperative effect between the formation of nano-CuO and nano-ZnAl2O4 amorphous clusters facilitates the topochemical transformation of LDH to spinel due to the contribution of octahedral CuII vacancy to ZnII diffusion. © 2013 American Chemical Society.

Glycoalkaloid Content and Starch Structure in Solanum Species and Interspecific Somatic Potato Hybrids

When genome sections of wild Solanum species are bred into the cultivated potato (S. tuberosum L.) to obtain improved potato cultivars, the new cultivars must be evaluated for their beneficial and undesirable traits. Glycoalkaloids present in Solanum species are known for their toxic as well as for beneficial effects on mammals. On the other hand, glycoalkaloids in potato leaves provide natural protection against pests. Due to breeding, glycoalkaloid profile of the plant is affected. In addition, the starch properties in potato tubers can be affected as a result of breeding, because the crystalline properties are determined by the botanical source of the starch. Starch content and composition affect the texture of cooked and processed potatoes. In order to determine glycoalkaloid contents in Solanum species, simultaneous separation of glycoalkaloids and aglycones using reversed-phase high-performance liquid chromatography (HPLC) was developed. Clean-up of foliage samples was improved using a silica-based strong cation exchanger instead of octadecyl phases in solid-phase extraction. Glycoalkaloids alpha-solanine and alpha-chaconine were detected in potato tubers of cvs. Satu and Sini. The total glycoalkaloid concentration of non-peeled and immature tubers was at an acceptable level (under 20 mg/100 g of FW) in the cv. Satu, whereas concentration in cv. Sini was 23 mg/100 g FW. Solanum species (S. tuberosum, S. brevidens, S. acaule, and S. commersonii) and interspecific somatic hybrids (brd + tbr, acl + tbr, cmm + tbr) were analyzed for their glycoalkaloid contents using liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS). The concentrations in the tubers of the brd + tbr and acl + tbr hybrids remained under 20 mg/100 g FW. Glycoalkaloid concentration in the foliage of the Solanum species was between 110 mg and 890 mg/100 g FW. However, the concentration in the foliage of S. acaule was as low as 26 mg/100 g FW. The total concentrations of brd + tbr, acl + tbr, and cmm + tbr hybrid foliages were 88 mg, 180 mg, and 685 mg/100 g FW, respectively. Glycoalkaloids of both parental plants as well as new combinations of aglycones and saccharides were detected in somatic hybrids. The hybrids contained mainly spirosolanes, and glycoalkaloid structures having no 5,6-double bond in the aglycone. Based on these results, the glycoalkaloid profiles of the hybrids may represent a safer and more beneficial spectrum of glycoalkaloids than that found in currently cultivated varieties. Starch nanostructure of three different cultivars (Satu, Saturna, and Lady Rosetta), a wild species S. acaule, and interspecific somatic hybrids were examined by wide-angle and small-angle X-ray scattering (WAXS, SAXS). For the first time, the measurements were conducted on fresh potato tuber samples. Crystallinity of starch, average crystallite size, and lamellar distance were determined from the X-ray patterns. No differences in the starch nanostructure between the three different cultivars were detected. However, tuber immaturity was detected by X-ray scattering methods when large numbers of immature and mature samples were measured and the results were compared. The present study shows that no significant changes occurred in the nanostructures of starches resulting from hybridizations of potato cultivars.

Entsymaattisen hydrolyysin vaikutuksista mikrokiteisen selluloosan rakenteeseen

Cellulose can be used as a renewable raw material for energy production. The utilization requires degradation of cellulose into glucose, which can be done with the aid of enzymatic hydrolysis. In this thesis, various x-ray methods were used to characterize sub-micrometer changes in microcrystalline cellulose during enzymatic hydrolysis to clarify the process and factors slowering it. The methods included wide-angle x-ray scattering (WAXS), small-angle x-ray scattering (SAXS) and x-ray microtomography. In addition, the samples were studied with transmission electron microscopy (TEM). The studied samples were hydrolyzed by enzymes of the Trichoderma reesei species for 6, 24, and 75 hours, which corresponded to 31 %, 58 %, and 68 % degrees of hydrolysis, respectively. Freeze-dried hydrolysis residues were measured with WAXS, SAXS and microtomography, whereas some of them were re-wetted for the wet SAXS and TEM measurements. The microtomography measurements showed a clear decrease in particle size in scale of tens of micrometers. In all the TEM pictures similar cylindrical and partly ramified structures were observed, independent of the hydrolysis time. The SAXS results were ambiguous and partly imprecise, but showed a change in the structure of wet samples in scale of 10-30 nm. According to the WAXS results, the degrees of crystallinity and the crystal sizes remained the same. The gained results support the assuption, that the cellulosic particles are hydrolyzed mostly on their surface, since the enzymes are unable to penetrate into the nanopores of wet cellulose. The hydrolysis therefore proceeds quickly in easily accessible particles and leaves the unaccesible particles almost untouched. The structural changes observed in the SAXS measurements might correspond to slight loosening of the microfibril aggregates, which was seen only in the wet samples because of their different pore structure.

Periodically Clickable Polyesters: Study of Intrachain Self-Segregation Induced Folding, Crystallization, and Mesophase Formation

A series of polyesters based on 2-propargyl-1,3-propanediol or 2,2-dipropargyl-1,3-propanediol or 2-allyl-2-propargyl-1,3-propanediol and 1,20-eicosanedioic acid were prepared by solution polycondensation using the corresponding diacid chloride; these polyesters were quantitatively ``clicked'' with a fluoroalkyl, azide, namely CF3(CF2)(7)CH2CH2N3, to yield polyesters carrying long-chain alkylene segments in the backbone and either one or two perfluoroalkyl segments located at periodic intervals along the polymer chain. The immiscibility of the alkylene and fluoroalkyl segments causes the polymer chains to fold in a zigzag fashion to facilitate the segregation of these segments; the folded chains further organize in the solid state to form a lamellar structure with alternating domains of alkyl (HC) and fluoroalkyl (FC) segments. Evidence for the self-segregation is provided by DSC, SAXS, WAXS, and TEM studies; in two of the samples, the DSC thermograms showed two distinct endotherms associated with the melting of the individual domains, while the WAXS patterns confirm the existence of two separate peaks corresponding to the interchain distances within the crystalline lattices of the HC and FC domains. SAXS data, on the other hand, reveal the formation of an extended lamellar morphology with an interlamellar spacing that matches reasonably well with those estimated from TEM studies. Interestingly, a smectic-type liquid crystalline phase is observed at temperatures between the two melting transitions. These systems present a unique opportunity to develop interesting nanostructured polymeric materials with precise control over both the domain size and morphology; importantly, the domain sizes are far smaller than those typically observed in traditional block copolymers.

Structural evolution of tensile deformed high-density polyethylene at elevated temperatures: Scanning synchrotron small- and wide-angle X-ray scattering studies

The structural evolution of an ice-quenched high-density polyethylene (HDPE) subjected to uniaxial tensile deformation at elevated temperatures was examined as a function of the imposed strains by means of combined synchrotron small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS) techniques. The data show that when stretching an isotropic sample with the spherulitic structure, intralamellar slipping of crystalline blocks was activated at small deformations, followed by a stress-induced fragmentation and recrystallization process yielding lamellar crystallites with their normal parallel to the stretching direction. Stretching of an isothermally crystallized HDPE sample at 120 degrees C exhibited changes of the SAXS diagram with strain similar to that observed for quenched HDPE elongated at room temperature, implying that the thermal stability of the crystal blocks composing the lamellae is only dependent on the crystallization temperature.

Crystallization kinetics of poly(ether ether ketone) (PEEK) from its metastable melt

After isothermal crystallization of the amorphous poly(ether ether ketone), double endothermic behaviour can be found through differential scanning calorimetry experiments. During the heating scan of semicrystalline PEEK, a metastable melt, which comes from the melt of the thinner lamellar crystal populations, can be obtained between these two endotherms. The metastable melt can recrystallize immediately just above the lower melting temperature and form slightly thicker lamellae than the original ones. The thickness and the perfection depend upon the crystallization time and the crystallization temperature. By comparing the TEM morphological observations of the samples before and after partial melting, it can be shown that lamellar crystals, having different thermodynamic stability, form during isothermal crystallization. After partial melting, only the type of lamellar crystal exhibiting the higher thermodynamic stability remains. Wide angle X-ray diffraction measurements shows a slightly change in the crystallinity of the samples before and after the partial melting. Small angle X-ray scattering results exhibit a change in the long period of the lamellar crystals before and after the partial melting process. The crystallization kinetics of the metastable melt can be determined by means of differential scanning calorimetry. The kinetic analysis showed that the isothermal crystallization of the metastable PEEK melt proceeds with an Avrami exponent of n = 1.0 similar to 1.4, reflecting that probably one-dimensional or an irregular line growth of the crystal occurred between the existing main lamellae with heterogeneous nucleation. (C) 1998 Elsevier Science Ltd. All rights reserved.

Melt functionalization of ethylene-propylene copolymer: Structural investigation

An ethylene-propylene copolymer (EPM) has been functionalized with acrylic acid (AA) by means of a radical-initiated melt process. Different degrees of grafting have been obtained by varying the overall composition of the reaction mixture. The influence of the grafting degree on the structure has been investigated by differential scanning calorimetry (DSC), Fourier-transform infrared analysis (FTIR), and wide-angle x-ray scattering (WAXS) techniques. The results of the structural investigations suggest that the grafting preferentially occurs onto the ethylene sequences of EPM. After acrylic acid was grafted onto EPM, the grafted AA acted as nucleation agent; it caused an increase of crystallization temperature of propylene sequences of EPM-g-AA.

Inorganic glasses, glass-forming liquids and amorphizing solids

Greaves, George; Sen, S., (2007) 'Inorganic glasses, glass-forming liquids and amorphizing solids', Advances in Physics 56(1) pp.1-166 RAE2008

Multiaxial Deformation of Polyethylene and Polyethylene/Clay Nanocomposites: In Situ Synchrotron Small Angle and Wide Angle X-Ray Scattering Study

A unique in situ multiaxial deformation device has been designed and built specifically for simultaneous synchrotron small angle X-ray scattering (SAXS) and wide angle X-ray scattering (WAXS) measurements. SAXS and WAXS patterns of high-density polyethylene (HDPE) and HDPE/clay nanocomposites were measured in real time during in situ multiaxial deformation at room temperature and at 55 degrees C. It was observed that the morphological evolution of polyethylene is affected by the existence of clay platelets as well as the deformation temperature and strain rate. Martensitic transformation of orthorhombic into monoclinic crystal phases was observed under strain in HDPE, which is delayed and hindered in the presence of clay nanoplatelets. From the SAXS measurements, it was observed that the thickness of the interlamellar amorphous region increased with increasing strain, which is due to elongation of the amorphous chains. The increase in amorphous layer thickness is slightly higher for the nanocomposites compared to the neat polymer. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 669-677, 2011

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.