Solid–Liquid Phase Behaviors of Binary Mixtures of Various Partial Acylglycerols by Differential Scanning Calorimetry

Monoacylglycerol (MAG), diacylglycerol (DAG), and triacylglycerol (TAG) are impurities in biodiesel and a major cause of precipitation. Understanding the behavior of such acylglycerols is essential for predicting biodiesel cold flow properties (CFPs). The previous study on MAG/MAG binary mixtures shows that they tend to solidify by forming molecular compounds. In contrast, TAG/TAG mixtures, which have been studied extensively, are commonly eutectic or monotectic systems, in which each component solidifies separately. The present study focuses on binary mixtures of DAG/DAG and different acylglycerol pairs (MAG/DAG, TAG/MAG, and DAG/TAG), and determination of their solid–liquid phase behavior by differential scanning calorimetry. These mixtures are found to behave as eutectic or monotectic systems with no sign of compound formation. As DAG and TAG have lower contents than MAG in biodiesel and they are unlikely to form molecular compounds with MAG, it is suggested that DAG and TAG have little effect on the biodiesel CFPs. Practical Applications: Biodiesel has attracted much interest because its blending with conventional fossil diesel has become more standard with biofuel mandates. From an energy perspective, the solid–liquid phase behavior of acylglycerols will contribute to building prediction models for biodiesel CFPs.     

Melt-mixing by novel pitched-tip kneading disks in a co-rotating twin-screw extruder

Melt-mixing in twin-screw extruders is a key process in the development of polymer composites. Quantifying the mixing performance of kneading elements based on their internal physical processes is a challenging problem. We discuss melt-mixing by novel kneading elements called “pitched-tip kneading disk (ptKD)”. The disk-stagger angle and tip angle are the main geometric parameters of the ptKDs. We investigated four typical arrangements of the ptKDs, which are forward and backward disk-staggers combined with forward and backward tips. Numerical simulations under a certain feed rate and screw revolution speed were performed, and the mixing process was investigated using Lagrangian statistics. It was found that the four types had different mixing characteristics, and their mixing processes were explained by the coupling effect of drag flow with the disk staggering and pitched-tip and pressure flows, which are controlled by operational conditions. The use of a pitched-tip effectively controls the balance of the pressurization and mixing ability.     

Shape memory properties of polypeptide hydrogels having hydrophobic alkyl side chains

Polypeptide hydrogels were prepared by cross-linking of hydrophobically-modified poly[N⁵-(2-hydroxyethyl) l-glutamine] having alkyl side chains –C_nH_2n+1. Chain length of the alkyl group was n = 8, 16, and 18, and their mole fractions in the polypeptide were varied in the range of 0.05–0.16. Shape memory ability of the prepared polypeptide hydrogels was investigated. After deformation at 60 °C, the hydrogel was cooled in order to fix the temporary deformed shape. It was found that crystallization of the alkyl side chains did not occur, and the fixation ability of the hydrogel at 0 °C was low. In the subsequent heating process, the deformed temporary shape spontaneously recovered to the original shape gradually with increasing temperature, in other words, the shape recovery ratio varied with depending on the recovery temperature. From these observations, it was proposed that the shape fixation of the polypeptide hydrogel was achieved by strong segregation of the hydrophobic alkyl chains at low temperature, and the shape recovery of the deformed hydrogel was accompanied by the gradual decrease of the segregation strength with the temperature increase.     

Insights from ab initio molecular dynamics simulations for a multicomponent oxide glass

It remains a challenge to establish structural models of multicomponent oxide glass systems. In this study, we have investigated 68.3SiO₂–16.1B₂O₃–4.2Al₂O₃–11.4Na₂O glass and melt structures by ab initio molecular dynamics (AIMD) simulations. The atomic configurations obtained from AIMD simulations were validated against ¹⁷O solid‐state NMR spectrum under 24.0 T and neutron diffraction data, and excellent agreement was achieved. The bond lengths, angles, and coordination geometries were statistically analyzed for each atomic species. Here we particularly address the role of minor atomic species such as five‐coordinate Si (Si^V) and Al (Al^V). The Si^V–O bond lengths and O–Si^V–O angle distribution in the glass indicated 1.718 Å and three peaks at 90°, 120°, and 175°, which are assigned to a coordination geometry of the trigonal bipyramidal structure. Ring statistic analysis revealed that Si^V and Al^V were found to preferentially contribute to the formation of small ring sizes.     

Preparation of flexible transparent acryl/alumina nano-hybrid materials exhibiting low thermal expansion coefficient

In this study, flexible transparent hybrid films with low thermal expansion coefficient were prepared by combination of alumina fillers and polymerizable/non-polymerizable surface modifiers with carboxyl group. Four types of alumina fillers with different shape and size were used in this study, and could modify with surface modifiers containing carboxyl groups by electrostatic interaction and disperse homogeneously in resulting hybrid films regardless of the shape and size. So the hybrid films obtained showed high transmittance around 90%T, and it was considered, from transmission electron microscopic analysis, alumina fillers were dispersed at near original filler size, without aggregation. Moreover, thermal mechanical analysis cleared that the use of pillar or fiber type filler is more effective to reduce CTE compared with plate type fillers, especially CTE of hybrid film prepared with fiber type filler was drastically decreased to 17 ppm/K, while the influence by the difference of filler shape/size was not observed on tensile properties, surface hardness. By use of fiber type alumina filler and combination of polymerizable surface modifier and non-polymerizable surface modifier which seems to interact with matrix, for optimizing of the crosslink density, it was possible to reduce CTE, while the good mechanical properties was kept. Finally, hybrid film indicating low CTE value as 19 ppm/K, high flexibility (windable against 0.4 mm radius steel bar), and good tensile properties and surface hardness which were equal to or higher than those of matrix could prepared.     

Approach from physicochemical aspects in membrane filtration

In membrane filtration, solution environment factors such as pH and solvent density are important in controlling the filtration rate and the rejection of the particles and/or the macromolecules. The filtration rate and the rejection in membrane filtration have been investigated from physicochemical aspects. It was shown that the properties of the filter cake formed on the membrane surface play a vital role in determining the filtration rate in mem-brane filtration. It was clearly demonstrated that such filtration behaviors as the filtration rate and the rejection are highly dependent on the electrical nature of the particles and/or the macromolecules. Furthermore, it was shown that the solvent density ρ has a large effect on the steady filtration rate in upward ultrafiltration.     

Predicting Solid–Liquid Equilibrium of Fatty Acid Methyl Ester and Monoglyceride Mixtures as Biodiesel Model Fuels

Fatty acid methyl esters from plant oils are the main component of biodiesel and used as a substitute for petroleum diesel. Biodiesel generally contains a small amount of monoglycerides as intermediate compounds, which have high melting points and often solidify and clog fuel filters. The prediction of the cold-flow property of biodiesel is of great importance for practical application. In this study, a thermodynamic study was conducted for mixtures of monoglycerides and fatty acid methyl esters. Temperatures of the solid–liquid equilibrium for the mixtures were measured by differential scanning calorimetry and visual observation, while the theoretical values were calculated using the modified Universal Quasi-chemical Functional-group Activity Coefficients (UNIFAC) model (Dortmund). The theoretical and experimental results were in good agreement, especially for binary mixtures of monoglycerides and methyl esters. The importance of monoglycerides on the cold-flow properties of biodiesel was determined, and the effects could be well described by the modified UNIFAC model (Dortmund).     

Differential Scanning Calorimetric Study of Solidification Behavior of Monoacylglycerols to Investigate the Cold-Flow Properties of Biodiesel

Monoacylglycerols (MAG) are impurities present in biodiesel as a result of incomplete reactions. MAG often solidify in biodiesel even at room temperature because of their high melting points. This worsens the cold-flow properties such as the cloud point and pour point. We hypothesized that several types of MAG solidify simultaneously; therefore, we performed differential scanning calorimetry of binary mixtures of MAG to elucidate their interactions during solidification. Three thermodynamic formulas were then applied to the experimental results: (1) non-solid-solution, (2) solid-solution, and (3) compound formation models. Binary mixtures of MAG showed complicated liquidus curves with multiple upward convex shapes, with which only the compound formation model fitted well. This model was applied to multicomponent mixtures that consisted of MAG and fatty acid methyl esters (FAME) as surrogate biodiesel fuels. We confirmed that the model still worked well. The results show that the compound formation model has good potential for predicting the cold-flow properties of biodiesel.