Novel differential scanning calorimetry (DSC) application to select polyhydroxyalkanoate (PHA) producers correlating 3-hydroxyhexanoate (3-HHx) monomer with melting enthalpy.

Polyhydroxyalkanoate (PHA) is an environmental alternative to petroleum-based plastics because of its biodegradability. The polymer properties of PHA have been improved by the incorporation of different monomers. Traditionally, the monomer composition of PHA has been analyzed using gas chromatography (GC) and nuclear magnetic resonance (NMR), providing accurate monomer composition. However, sequential analysis of the thermal properties of PHA using differential scanning calorimetry (DSC) remains necessary, providing crucial insights into its thermal characteristics. To shorten the monomer composition and thermal property analysis, we directly applied DSC to the analysis of the obtained PHA film and observed a high correlation (r2 = 0.98) between melting enthalpy and the 3-hydroxyhexanoate (3-HHx) mole fraction in the polymer. A higher 3-HHx fraction resulted in a lower melting enthalpy as 3-HHx provided the polymer with higher flexibility. Based on this, we selected the poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P(3HB-co-3HHx)) producing strain from Cupriavidus strains that newly screened and transformed with vectors containing P(3HB-co-3HHx) biosynthetic genes, achieving an average error rate below 1.8% between GC and DSC results. Cupriavidus sp. BK2 showed a high 3-HHx mole fraction, up to 10.38 mol%, with Tm (℃) = 171.5 and ΔH of Tm (J/g) = 48.0, simultaneously detected via DSC. This study is an example of the expansion of DSC for PHA analysis from polymer science to microbial engineering.

Physical-Entanglements-Supported Polymeric Form Stable Phase Change Materials with Ultrahigh Melting Enthalpy.

With the rapid development of new energy and the upgrading of electronic devices, structurally stable phase change materials (PCMs) have attracted widespread attentions from both academia and industries. Traditional cross-linking, composites, or microencapsulation methods for preparation of form stable PCMs usually sacrifice part of the phase change enthalpy and recyclability. Based on the basic polymer viscoelasticity and crystallization theories, here, a kind of novel recyclable polymeric PCM is developed by simple solution mixing ultrahigh molecular weight of polyethylene oxide (UHMWPEO) with its chemical identical oligomer polyethylene glycol (PEG). Rheological and leakage-proof experiments confirm that, even containing 90% of phase change fraction PEG oligomers, long-term of structure stability of PCMs can be achieved when the molecular weight of UHMWPEO is higher than 7000 kg mol-1 due to their ultralong terminal relaxation time and large number of entanglements per chain. Furthermore, because of the reduced overall entanglement concentration, phase change enthalpy of PCMs can be greatly promoted, even reaching to ≈185 J g-1, which is larger than any PEG-based form stable PCMs in literatures. This work provides a new strategy and mechanism for designing physical-entanglements-supported form stable PCMs with ultrahigh phase change enthalpies.

Probing the Melting Transitions in Phase-Change Superlattices via Thin Film Nanocalorimetry.

Phase-change superlattices with nanometer thin sublayers are promising for low-power phase-change memory (PCM) on rigid and flexible platforms. However, the thermodynamics of the phase transition in such nanoscale superlattices remain unexplored, especially at ultrafast scanning rates, which is crucial for our fundamental understanding of superlattice-based PCM. Here, we probe the phase transition of Sb2Te3 (ST)/Ge2Sb2Te5 (GST) superlattices using nanocalorimetry with a monolayer sensitivity (∼1 Å) and a fast scanning rate (105 K/s). For a 2/1.8 nm/nm Sb2Te3/GST superlattice, we observe an endothermic melting transition with an ∼240 °C decrease in temperature and an ∼8-fold decrease in enthalpy compared to those for the melting of GST, providing key thermodynamic insights into the low-power switching of superlattice-based PCM. Nanocalorimetry measurements for Sb2Te3 alone demonstrate an intrinsic premelting similar to the unique phase transition of superlattices, thus revealing a critical role of the Sb2Te3 sublayer within our superlattices. These results advance our understanding of superlattices for energy-efficient data storage and computing.

Prediction of Second Melting Temperatures Already Observed in Pure Elements by Molecular Dynamics Simulations.

A second melting temperature occurs at a temperature Tn+ higher than Tm in glass-forming melts after heating them from their glassy state. The melting entropy is reduced or increased depending on the thermal history and on the presence of antibonds or bonds up to Tn+. Recent MD simulations show full melting at Tn+ = 1.119Tm for Zr, 1.126Tm for Ag, 1.219Tm for Fe and 1.354Tm for Cu. The non-classical homogeneous nucleation model applied to liquid elements is based on the increase of the Lindemann coefficient with the heating rate. The glass transition at Tg and the nucleation temperatures TnG of glacial phases are successfully predicted below and above Tm. The glass transition temperature Tg increases with the heating rate up to Tn+. Melting and crystallization of glacial phases occur with entropy and enthalpy reductions. A universal law relating Tn+ and TnG around Tm shows that TnG cannot be higher than 1.293Tm for Tn+= 1.47Tm. The enthalpies and entropies of glacial phases have singular values, corresponding to the increase of percolation thresholds with Tg and TnG above the Scher and Zallen invariant at various heating and cooling rates. The G-phases are metastable up to Tn+ because the antibonds are broken by homogeneous nucleation of bonds.

Correlation between Mechanical and Thermal Properties of Human Hair.

CONTEXT: Hair strength depends on integrity of protein structure, aging, and chemical effects and its exposure to mechanical (combing and curling) and thermal (hair drying and straightening) stimuli. AIMS: The aim of this study is to correlate the mechanical properties such as tensile yield stress and tensile modulus of single hair fibers with thermal properties such as melting enthalpy and melting point obtained by differential scanning calorimetry. MATERIALS AND METHODS: Single hair fibers covering seven decades of age were cut 2 cm above the scalp. Tensile specimens were prepared using single fibers with gauge length of 20 mm, and test was carried out with speed of 20 mm/min. For thermal analysis, 2-3 mg of hair samples were cut to 0.5 mm length and loaded in aluminum pan and heated at a rate of 10°C/min from 30°C to 280°C. DATA ANALYSIS: Tensile yield stress (determined at the onset of stress constancy at ~3% strain) and tensile modulus were determined using Origin software. The same software was used to plot the thermal data as heat flow (W/g)-temperature diagrams and to determine the peak temperature and peak area (melting enthalpy) by creating a sigmoidal baseline. RESULTS: The typical values of tensile modulus, yield stress, and maximum stress obtained were 5.1 ± 0.5 GPa, 109 ± 9 MPa, and 161 ± 24 MPa, respectively. Further, typical values of melting enthalpy and peak temperature determined were 6.29 ± 0.20 J/g and 235°C ± 0.6°C, respectively. CONCLUSIONS: Mechanical yield stress and melting enthalpy were compared, and it was found that a good nonlinear (sigmoidal) correlation was obtained. The nonlinear correlation seems to provide an accurate representation of a composite keratin structure wherein the % crystallinity exhibits a range, and also, crystalline and amorphous regions are intertwined and intricate in nature.

Production, optimization and characterization of polyhydroxybutyrate, a biodegradable plastic by Bacillus spp.

Poly-ß-hydroxybutyrate (PHB) is the intracellular lipid reserve accumulated by many bacteria. The most potent terrestrial bacterium Bacillus cereus SE-1 showed more PHB accumulating cells (22.1 and 40% after 48 and 72 h) than that of the marine Bacillus sp. CS-605 (5 and 33% after 48 and 72 h). Both the isolates harbored phbB gene and the characteristics C=O peak was observed in the extracted PHB by Fourier transformed infrared spectroscopy analysis. Maltose was found to be the most suitable carbon source for the accumulation of PHB in B. cereus SE-1. The extracted PHB sample from B. cereus SE-1 was blended with a thermoplastic starch (TS) and an increased thermoplasticity and decreased crystallinity were observed after blending in comparison to the standard PHB. The melting temperature (Tm), melting enthalpy (∆Hf), and crystallinity (Xc) of the blended PHB sample were found to be 109.4 °C, 64.58 J/g, and 44.23%, respectively.

Rheological of chocolate-flavored, reduced-calories coating as a function of conching process.

Continuous flow and linear viscoelasticity rheology of chocolate coating is studied in this work using fat substitute gums (xanthan, GX). An alternative conching process, using a Rotor-Estator (RE) type impeller, is proposed. The objective is to obtain a chocolate coating material with improved flow properties. Characterization of the final material through particle size distribution (PSD), differential scanning calorimetry (DSC) and proximal analysis is reported. Particle size distribution of the final material showed less polydispersity and therefore, greater homogeneity; fusion points were also generated at around 20 °C assuming crystal type I (ß'2) and II (α). Moreover, the final material exhibited crossover points (higher structure material), whereas the commercial brand chocolate used for comparison did not. The best conditions to produce the coating were maturing of 36 h and 35 °C, showing crossover points around 76 Pa and a 0.505 solids particle dispersion (average particle diameter of 0.364 µm), and a fusion point at 20.04 °C with a ΔHf of 1.40 (J/g). The results indicate that xanthan gum is a good substitute for cocoa butter and provides stability to the final product.

The impact of baking time and bread storage temperature on bread crumb properties.

Two baking times (9 and 24 min) and storage temperatures (4 and 25 °C) were used to explore the impact of heat exposure during bread baking and subsequent storage on amylopectin retrogradation, water mobility, and bread crumb firming. Shorter baking resulted in less retrogradation, a less extended starch network and smaller changes in crumb firmness and elasticity. A lower storage temperature resulted in faster retrogradation, a more rigid starch network with more water inclusion and larger changes in crumb firmness and elasticity. Crumb to crust moisture migration was lower for breads baked shorter and stored at lower temperature, resulting in better plasticized biopolymer networks in crumb. Network stiffening, therefore, contributed less to crumb firmness. A negative relation was found between proton mobilities of water and biopolymers in the crumb gel network and crumb firmness. The slope of this linear function was indicative for the strength of the starch network.

Interfacial behaviour of sodium stearoyllactylate (SSL) as an oil-in-water pickering emulsion stabiliser.

The ability of a food ingredient, sodium stearoyllactylate (SSL), to stabilise oil-in-water (O/W) emulsions against coalescence was investigated, and closely linked to its capacity to act as a Pickering stabiliser. Results showed that emulsion stability could be achieved with a relatively low SSL concentration (≥0.1 wt%), and cryogenic-scanning electron microscopy (cryo-SEM) visualisation of emulsion structure revealed the presence of colloidal SSL aggregates adsorbed at the oil-water interface. Surface properties of SSL could be modified by altering the size of these aggregates in water; a faster decrease in surface tension was observed when SSL dispersions were subjected to high pressure homogenisation (HPH). The rate of SSL adsorption at the sunflower oil-water interface also increased after HPH, and a higher interfacial tension (IFT) was observed with increasing SSL concentration. Differential scanning calorimetry (DSC) enabled a comparison of the thermal behaviour of SSL in aqueous dispersions with SSL-stabilised O/W emulsions. SSL melting enthalpy depended on emulsion interfacial area and the corresponding DSC data was used to determine the amount of SSL adsorbed at the oil-water interface. An idealised theoretical interfacial coverage calculation based on Pickering emulsion theory was in general agreement with the mass of SSL adsorbed as predicted by DSC.