Light transmission and the fine structure of poly(methyl methacrylate) nanofibers and films

In this paper, the structure and optical properties of poly(methyl methacrylate) (PMMA) nanofibers and films were investigated. Differential scanning calorimetery (DSC) and Wide-Angle X-ray scattering (WAXS) results confirmed the amorphous structure of both nanofibers and films. Low angle X-ray diffraction (LA-XRD) revealed the presence of voids and/or particles with the spacing of 128.4 Å within the nanofibers. From the Porod plots, a three-dimensional surface fractal for the nanofibers and a mass fractal structure for the films were derived. By the interpretation of Small Angle X-ray scattering (SAXS), the shape and size of the particles in the samples were assessed. It was concluded that the particles shape within the nanofibers and the films were globular, with the radius of gyration of 8.5 nm for the nanofibers and 16.5 nm for the films. The nanofiber mat showed less light transparency when compared with the film. This phenomenon could be attributed to the difference in the physical shape, as well as scattering of the light by the voids or particles within the nanofibers.     

Properties of Frozen Wheat Doughs at Subzero Temperatures

The subzero properties of wheat doughs were measured by dynamic mechanical thermal analysis (DMTA) and dielectric thermal analysis (DETA) over the temperature range −90 to +40 °C and by¹H-nuclear magnetic resonance (NMR) T₂relaxation over the range −45 to 0 °C. The experiments revealed two transitions in the dough: one independent of frequency at −10 °C (attributed to ice melting) and one dependent on frequency at −30 °C (attributed to a glass transition). The glass transition temperatures measured by DMTA moved to higher temperatures during frozen storage when the optimal water content of dough was used. A reduction in the water content eliminated this phenomenon. A similar effect of water reduction was observed by NMR studies, in which amplitude ratios and decay times were used to calculate the phase transitions. However, the glass transition recorded by NMR was independent of frozen storage with optimal water content. The changes of water state in frozen doughs were studied by ultracentrifugation (the amount of liquid phase) and NMR (freezable water based on liquid amplitude ratios). Frozen storage increased the liquid phase in dough with optimal water content. Thus, ice crystals are growing during frozen storage resulting in the concentration of polymers and a higher glass transition observed by DMTA. The increase of liquid phase during storage was substantially lower when the water content of dough was decreased. Ice crystals» growth can be minimised by reducing water content. The experiments were carried out with four different flours. The measurement of glass transition temperature by DMTA, DETA or NMR did not reveal great differences in doughs made from different flours. The amount of liquid phase was strongly flour dependent.     

Spinodal phase separation and isothermal crystallization behavior in blends of VDF/TrFE(75/25) copolymer and poly(1,4-butylene adipate) (I)

Phase behavior and spinodal phase separation kinetics in binary blends of a random copolymer of vinylidene fluoride and trifluoroethylene (75/25) [P(VDF/TrFE)] and poly(1,4-butylene adipate) (PBA) have been investigated by means of optical microscopic observation and time-resolved light scattering. The blends exhibited a typical lower critical solution temperature (LCST)∼34 °C above the melting temperature of the P(VDF/TrFE) crystals over the entire blend composition range. P(VDF/TrFE) and PBA were totally miscible in the temperature gap between the melting point of P(VDF/TrFE) and the LCST. Temperature jump experiments of the 3/7 P(VDF/TrFE)/PBA blend were carried out on a light-scattering apparatus from a single-phase melt state (180 °C) to a two-phase region (205∼215 °C). Since the late stage of spinodal decomposition (SD) is prevalent in the 3/7 blend, SD was analyzed using a power law scheme. Self-similarity was preserved well in the late stage of SD in the 3/7 blend.     

Study of microstructure of oriented PET fibres exposed to supercritical carbon dioxide

Samples of partially oriented yarn (POY) PET fibers were uniaxially drawn at temperatures below, near, and above the glass transition temperature at a constant draw ratio before exposure to supercritical carbon dioxide (scCO₂) in the presence of tension at a temperature of 80 °C and a pressure of 220 bar. The effects of drawing temperature and scCO₂ exposure on structural changes and on mesomorphic transitions, in particular, were investigated using differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and birefringence and density measurements. A good correlation was obtained among the results obtained from various techniques. Results indicated that the development of a transient mesophase structure depended strongly on process temperature. By drawing PET fibers in the samples at temperatures below the glass transition (cold-drawing), a mesophase structure developed in which the highly extended chains played a key role in structural changes incurred. Meanwhile, exposure to scCO₂ led to the plasticization of the samples accompanied by their reduced glass transition and cold crystallization temperatures. This process also gave rise to the appearance of a second melting peak at about 135 °C that is related to the melting of imperfect and thin crystals, thereby inducing structural changes in the treated fibers. In the case of samples subjected to cold drawing and to scCO₂ exposure, the transformation of the mesophase structure into the crystalline phase was found to be strongly affected by scCO₂ exposure, while this same effect was negligible in the case of hot drawn samples.     

Preparation and characterization of thermoplastic polyurethanes using partially acetylated kraft lignin

Thermoplastic polyurethanes were prepared using 90 % acetylated softwood kraft lignin, polyethylene glycol and 4,4-methylene diphenyl diisocyanate. Due to the glass transitions of the compatible soft and hard segment mixtures, the polyurethanes exhibited the first glass transitions at ?40 to 10 °C, and the transition temperatures increased with increasing hard segment content. Due to the glass transitions of the microphase separated hard domains, the second glass transitions occurred at 150 °C. The viscous responses during the second transitions decreased as the separated hard domains-induced chemical and physical crosslinks increased. The Young’s modulus and tensile strength increased with increasing hard segment content, whereas the breaking strain decreased. The phase morphology changed from an isolated hard domain structure to an interconnected one as the physical crosslinks increased, which caused drastic changes in the increasing or decreasing tendency of the tensile strength or breaking strain. Because of the phase morphology, the polyurethanes exhibited viscoplasticity or viscoelasticity.     

Mechanical and moisture absorption characterization of PLA composites reinforced with nano-coated flax fibers

This research is intended to improve the interface between the fibers and the matrix and limit water absorption of bio-based material thereby decreasing degradation of the composites when they are exposed to external environment such as high temperature and humidity. In this study, flax fibers were treated with an organic surface coating containing SiO₂ nanoparticles. This coating was a dispersion of silica fume in epoxy. One composite was also made with raw fibers as reference as well as one sample of pure PLA. Flax fibers/PLA composites were manufactured by hot pressing by stacking 4 PLA films and 3 pieces of flax fabric. Morphology and dispersion of the coating on the fibers was observed by scanning electron microscopy (SEM), small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). Accelerated ageing was carried out on the 3 materials by placing them in a 50 °C water bath until saturation to investigate the influence of the coating on water diffusion. Mechanical properties of the different composites were investigated by tensile (before and after conditioning) and short beam shear (SBS) testing in order to evaluate the impact of the coating on the interfacial properties of the materials. The results show that the fibers surface was homogenized and that a better adhesion was reached because of the coating. Coating the fibers also allowed the decrease in water uptake by more than 10 % and their protection during conditioning, preserving their mechanical properties.     

Thermally induced phase separation in supported bilayers of glycosphingolipid and phospholipid mixtures

The authors have studied microstructure evolution during thermally induced phase separation in a class of binary supported lipid bilayers using a quantitative application of imaging ellipsometry. The bilayers consist of binary mixtures consisting of a higher melting glycosphingolipid, galactosylceramide (GalCer), which resides primarily in the outer leaflet, and a lower melting, unsaturated phospholipid, 1,2-dilauroyl-sn-glycero-3-phosphocholine (DLPC). Three different bilayer compositions of GalCer/DLPC mixtures at 35:65, 20:80, and 10:90 molar ratios were cooled at controlled rates from their high-temperature homogeneous phase to temperatures corresponding to their phase coexistence regime and imaged in real time using imaging ellipsometry. During the thermotropic course of GalCer gelation, we find that two distinct types of morphological features modulate. First, the formation and growth of chain and fractal-like defects ascribed to the net change in molecular areas during the phase transition. The formation of these defects is consistent with the expected contraction in the molecular area during the liquid crystalline to gel-phase transition. Second, the nucleation and growth of irregularly shaped gel-phase domains, which exhibit either line-tension dominated compact shape or dendritic domains with extended interfaces. Quantifying domain morphology within the fractal framework reveals a close correspondence, and the quantization of the transition width confirms previous estimates of reduced phase transition cooperativity in supported bilayers. A comparison of domain properties indicates that thermal history, bilayer composition, and cooling rate all influence microstructure details including shapes, sizes, and distributions of domains and defects: At lower cooling rates and lower GalCer fractions compact domains form and at higher GalCer fractions (or at higher cooling rates) dendritic domains are evident. This transition of domain morphology from compact shapes to dendritic shapes at higher cooling rates and higher relative fractions of GalCer suggests kinetic control of shape equilibration in these phospho- and glycolipid mixtures.     

Effect of thermal packaging temperature on Chinese steamed bread quality during room temperature storage

In order to investigate the influence of different packaging temperature on thermal-vacuum packaged Chinese steamed bread (CSB) quality under room temperature storage, the packaging temperatures of 50 °C, 70 °C and 90 °C were set respectively to study the effect on the packaging vacuum degree (VD) and starch retrogradation properties. The VD and moisture content of thermal-vacuum packaged CSB significantly increased with the increase of the packaging temperature from 50 °C to 90 °C, while the hardness of CSB decreased, and there was no significant difference in moisture migration during room temperature storage. The results of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and small angle X-ray scattering (SAXS) indicated that CSB packaged at different temperatures formed B-type crystals, leading to an enhanced the ordered and dense state of starch structure, and the semi-crystalline growth ring structure disappeared during storage. The influence of different packaging temperatures on VD of CSB could effectively hinder the formation of ordered and dense state of CSB starch, consequently delaying the crystallization of amylopectin and inhibiting the progress of staling. The result of this study is of great significance for improving the quality of starchy foods and guiding the industrial development of Chinese steamed bread.     

Structural aspects of alkali treated sisal fiber — A SAXS investigation

The present work emphasizes the effect of alkali (NaOH) solution on macromolecular parameters of sisal fiber. The macromolecular parameters of alkali treated sisal fiber were computed along with air-dried sisal fiber by treating fiber as a non-ideal two-phase system characterized by continuous variation of electron density at the phase boundary. Small angle Xray scattering (SAXS) technique was employed to evaluate the macromolecular parameters, using correlation functions, applying the theories of Vonk, Ruland and Misra et al. The finite value of width of transition layer suggests to treat the fiber to be a non-ideal two-phased system. The evaluated macromolecular parameters are: transversal periodicity, specific inner surface, volume fractions of matter and void phases, transversal lengths in both phases, range of inhomogeneity, volume fraction of transition layer and length of coherence.     

Mechanical properties and crystal structure transition of biodegradable poly(butylene succinate-co-terephthalate) (PBST) fibers

Mechanical properties of biodegradable poly(butylene succinate-co-terephthalate) (PBST) fibers with 70 mol% butylene terephthalate (BT) were intensively investigated. Chemical structure composed of hard BT units and soft butylene succinate (BS) units made contributions to the higher elongation at break and lower initial modulus of PBST fibers than poly(butylene terephthalate) (PBT) fibers. Moreover, PBST fibers had better elastic properties than PBT fibers by exploring their elastic recovery. The stretch elastic recovery mechanism of PBST fibers was clarified from the point of crystal structure transition. According to the preliminary studies by wide angle X-ray diffraction (WAXD) measurements, two polymorphs (α form and β form) were confirmed when PBST fibers were applied to different deformations. With the help of intensive study by small angle X-ray scattering (SAXS) measurements, the crystal structure transition of PBST fibers was further verified.     

Dough/crumb transition during French bread baking

The modifications occurring during dough to crumb (D/C) transition of French bread (350 g) were studied in an instrumented pilot-scale oven for doughs with different contents of minor components, soluble, lipids and puroindolines. Internal temperature measurements showed that, for most compositions, complete D/C transition occurred between 55 and 70 °C, after 5 min of baking, and coincided with maximum loaf expansion. Differential scanning calorimetry (DSC) in excess of water performed on samples taken during baking (3 and 5 min) showed that starch gelatinization and melting developed continuously during D/C transition for various contents of the soluble fraction in dough. Dynamic thermomechanical analysis (DMA) on dough showed that dough stiffened between 60 and 70 °C, as seen by the increase of elastic modulus E′ by more than one decade, for all dough compositions. Relating these changes to the results of baking experiments, D/C transition was assigned first to gluten reticulation and, to a lesser extent, to continuous starch granule swelling.     

Sythesis and self-assembly of amphiphilic diblock rod-coil molecule consisting of biphenyl unit and poly(ethylene oxide) segment

A diblock rod-coil aromatic amphiphilic molecule, consisting of three biphenyls and one styrene unit linked together with ether bonds as a rigid rod segment and poly(ethylene oxide) with the number of repeating units of 34 as coil segment, has been synthesized. The self-assembling behavior of the molecule is investigated by means of differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), dynamic light scattering (DLS) and scanning electron microscope (SEM) in the solid state or an aqueous solution. This molecule spontaneously self-assembles into lamellar structure in the crystalline phase. In aqueous medium, the molecule self-organizes into spherical micelles and the micelles can be used as nanoreactor for Suzuki coupling reaction at room temperature.     

Synthesis of polypropylene carbonate polyol-based waterborne polyurethane modified with polysiloxane and its film properties

Waterborne polyurethane (WPU) prepolymer was synthesized using polypropylene carbonate polyol as the soft segment, dimethylolpropionic acid as a hydrophilic chain extender and isophorone diisocyanate. The prepolymer was modified with aminoethyl aminopropyl dimethicon (AEAPS) to prepare a series of WPU emulsions and films. The structures and the films properties of the WPUs were characterized by Fourier transform infrared spectrometry, gel permeation chromatography, atomic force microscopy, X-ray diffraction, thermogravimetric analysis, dynamic thermomechanical analysis, X-ray photoelectron spectroscopy, water contact angles and water absorption. It was found that pure polypropylene carbonate WPU had a wide molecular weight distribution and its microphase separation was not apparent between its hard and soft segments. The WPU also had a high glass transition temperature (24.5 °C) and its film had a high damping property (tan δ>0.40) from 12 °C to 42 °C. Modification with polysiloxane had enlarged the molecular weight, narrowed the molecular weight distribution and resulted in the microphase separation between the hard and soft segments of WPUs, and this amplified the damping temperature of the WPU films. Along with the increasing utilization of polysiloxane the thermolysis, water resistance and water contact angles of WPU films were improved while the orientation of their structure regularity declined.     

Characterization and mechanical properties of prepolymer and polyurethane block copolymer with a shape memory effect

The prepolymer and the final polyurethane (PU) block copolymer were synthesized by reacting 4,4-methylene bis(phenylisocyanate) with poly(tetramethylene glycol) and the prepolymer with 1,4-butanediol as a chain extender, respectively, to investigate the relation between phase separation and it’s resulting properties. According to FT-IR data, the phase separation of hard and soft segments in the prepolymer and the PU block copolymer grew bigger by increasing the hard segment content, and the PU showed more dominant phase separation than the prepolymer. The heat of fusion due to soft segments decreased in both the prepolymer and the PU by increasing the hard segment content, whereas the heat of fusion due to hard segments increased in the PU did not appear in the prepolymers. The breaking stress and modulus of the prepolymer increased by increasing the hard segment content, and the elongation at break decreased gradually, and the PU showed the highest breaking stress and modulus at 58 % hard segment content. However, the best shape recovery of the PU was obtained at 47 % hard segment content due to the existence of proper interaction among the hard segments for shape memory effect. Consequently, the mechanical properties and shape memory effect of the PU were influenced by the degree of phase separation, depending on the incorporation of chain extender as well as the hard segment content.     

Grafting of Triphenylmethyl Group onto Polyurethane and the Impact on the Shape Recovery and Flexibility at Extremely Low Temperature

The bulky and rigid triphenylmethyl group was grafted onto polyurethane (PU) to reduce the molecular attractions between hard segments and to improve the mobility of the PU chain under freezing conditions. The triphenylmethyl-grafted PU exhibited improvement in the cross-link density, solution viscosity, maximum tensile stress, shape recovery at 10 °C, and low temperature flexibility compared with the plain PU. The soft segment melting was not affected by the grafted triphenylmethyl group, whereas the soft segment crystallization disappeared with the increase of the triphenylmethyl group content. The glass transition temperature (T_g) increased with the increase of the triphenylmethyl group content. The rapid increase of the tensile strength and shape recovery at 10 °C resulted from the cross-linking effect, whereas the strain at break and shape retention at -25 °C slightly decreased with the increase of the triphenylmethyl group content. The triphenylmethylgrafted PU displayed an excellent low temperature flexibility even at -50 °C due to the improved mobility of the PU chain compared to ordinary PU.     

Changes in the thermal and structural properties of maize starch during nixtamalization and tortilla-making processes as affected by grain hardness

The objective of this work was to evaluate the changes in the thermal and structural properties of maize starch during nixtamalization and the tortilla-making process and their relationship with grain hardness. Three maize types with varying hardness (hard, intermediate, soft) were processed by three nixtamalization processes (classic, traditional and ecological). Starch from the three maize types showed an A-type pattern and two endotherms corresponding to gelatinization and melting of the Type I amylose-lipid complexes. After cooking and steeping, in intermediate and soft grains the partial gelatinization and the annealing affected the starch properties and promoted the formation of amylose-lipid complexes. These effects were not observe in hard grains. The increase in melting enthalpy and the intensity of the peak 2θ∼20° from nixtamal to tortillas demonstrated the formation of amylose-lipid complexes. A third endotherm above 114 °C in some treatments of nixtamal and tortilla starch demonstrated the transformation of some amylose-lipid complexes in a most ordered structures (Type II complexes). The V-type polymorph structure found in native starch, nixtamal, and tortilla corresponds to a coexistence of Type I and Type II complexes. Formation of amylose-lipid complexes in tortillas had a partial effect on decreasing starch retrogradation (r = −0.47, P < 0.05).     

Physicochemical, Rheological and Structural Characteristics of Starch in Maize Tortillas

Fresh and stored maize (white and blue) tortillas were evaluated for physicochemical, rheological and structural characteristics assessed by calorimetry, x-ray diffraction, Fourier transform infrared (FTIR) spectroscopy, dynamic viscoelastic tests, and high-performance size-exclusion chromatography. Two endotherms were found in studies of fresh and stored tortillas. The low temperature endotherm (50–56 °C) was due to reorganized (retrograded) amylopectin, while the high temperature endotherm (105–123 °C) was attributed to retrograded amylose. The enthalpy value for the lower temperature transition was minor than that of the high temperature transition. Fresh tortillas showed an amorphous starch arrangement by x-ray diffraction study. Stored samples showed the presence of peaks at 2θ = 17o and 23o, indicating re-crystallization of starch components. FTIR results confirmed the development of higher levels of starch crystals during storage. Differences in the viscoelastic parameters were also observed between fresh and stored samples. At the longest storage times, white tortillas were more rigid than blue tortillas. Molar mass values for starch increased for both white and blue tortillas as storage time progressed, though relatively higher values were obtained for white tortillas. More starch reorganization occurred in white tortillas, in accordance to calorimetric, x-ray diffraction, FTIR and rheological results. These results corroborate that changes occurring in tortillas during storage are related to reorganization of starch components, and the maize variety more than the color plays an important role.     

Miscibility and crystallization behaviors of poly(trimethylene terephthalate)/poly(ethylene naphthalate) blends

Poly(trimethylene terephthalate) (PTT)/poly(ethylene naphthalate) (PEN) blends of various compositions were prepared by the solution-blending and melt-blending methods. The changes in miscibility and crystallization behaviors of the blends upon thermal treatment above the melting temperature of the blends at 280°C were investigated by using DSC, DMA,¹H NMR, and SAXS analyses. Without any thermal treatment, the blend systems were not miscible, and the thermal transitions, such as glass transition, cold crystallization, and crystal melting of the individual components were observed in the DSC and DMA analyses. With thermal treatment, though, they became miscible as the thermal transitions of each component disappeared and single glass transition peaks were observed in the thermal analysis. The chain randomness determined using¹H NMR spectroscopy revealed that thermal treatment at 280°C for more than 30 min brought about transesterification reactions between the PTT and PEN segments resulting in an increase in their miscibility. These results were confirmed by the small angle X-ray analysis conducted to determine the long period (L), the thickness of the crystalline lamella stack (l _c ), and the thickness of the amorphous region (l _a ). After short thermal treatment, the melt-blended sample followed the values for the individual components. However, with extended thermal treatment, the blend became homogeneous, possessing different crystalline morphologies which resulted in different values ofL, l _c , andl _a .     

Synthesis and characterization of polyurethane-based side-chain cholesteric liquid crystal polymers

Polyurethane-based side-chain cholesteric liquid crystalline polymers (ChLCPs) with variable clearing temperatures were synthesized in a two-step reaction. The chemical structures of ChLCPs were confirmed by FT-IR and ¹H-NMR spectroscopy. The mesogenic properties and phase transition behavior were investigated by means of differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and X-ray diffraction measurements. The DSC studies show that the melting temperature and isotropic transition temperature of the ChLCPs increased with the weight percentage of cholesterol in the polymer. POM shows that the ChLCPs had a distinct spherulite structure that melted at about 140 °C, and these results are consistent with those of the DSC studies. The thermogravimetric studies show that the ChLCPs were stable up to 200 °C, though there was a reduction in the thermal stability as the weight proportion of cholesterol and glycerol in the polymer increased.     

Thermal,rheological properties and microstructure of hydrated gluten as influenced by antifreeze protein from oat (Avena sativa L.)

This study examined the thermal, rheological properties and microstructure of hydrated gluten as influenced by oat antifreeze protein (AsAFP). The thermal properties of fresh hydrated gluten, including the melting temperature, freezing temperature, freezable water content and glass transition temperature, were determined. For hydrated gluten samples after freeze-thaw treatment, the change in melting performance and freezable water content were analyzed. The results showed that the addition of AsAFP increased the glass transition temperature and decrease the melting enthalpy and freezable water content of fresh hydrated gluten. The supplementation of AsAFP also influenced the melting performance of hydrated gluten after freeze-thaw treatment. The rheological properties showed that the addition of AsAFP inhibited the deterioration of the rheological properties of hydrated gluten. The secondary structure of the gluten proteins changed significantly, α-helix decreased and β-sheet increased. The microstructure of the hydrated gluten demonstrated that supplementation with AsAFP may protect the gluten matrix from disruption during freeze-thaw cycles.