Physical properties of oleogels fabricated by the combination of diacylglycerols and monoacylglycerols

Oleogelation is an efficient way to structure oil and reduce saturated fatty acids of lipid products. Multi-component gels are of particularly interest attributed to the ability to tune gel properties by alteration of the component proportions. In this study, monoacylglycerol (MAG) and diacylglycerol (DAG) are used as gelator mixture and the influence of the ratio of these two crystalline particles on the characteristics of oleogels was investigated. The crystallization and melting behavior, solid fat content (SFC), crystal morphology, polymorphism and mechanical properties of the oleogels were characterized. The oleogels with higher gelator level displayed higher oil binding ability and shorter crystal formation time. The oleogels with higher MAG ratio exhibited more blade-like crystals, and the mixed oleogels with MAG: DAG of 3:7 and 5:5 showed altered crystal morphology with finer crystal size and reduced crystallization enthalpies possibly due to the increased nucleation seeds promoted by MAG. The oleogels with high MAG level showed lower equilibrium SFC during isothermal crystallization but faster crystallization rate, higher hardness and elasticity. Therefore, by changing the ratio of DAG with MAG, the crystallization profile and rheological properties of oleogels can be tailored and used as traditional solid fat substitutes in lipid-based products.

Significantly Enhanced Crystallization of Poly(ethylene succinate-co-1,2-propylene succinate) by Cellulose Nanocrystals as an Efficient Nucleating Agent

Poly(ethylene succinate-co-1,2-propylene succinate) (PEPS) is a novel aliphatic biodegradable polyester with good mechanical properties. Due to the presence of methyl as a side group, the crystallization rate of PEPS is remarkably slower than that of the poly(ethylene succinate) homopolymer. To promote the potential application of PEPS, the effect of cellulose nanocrystals (CNC) on the crystallization behavior, crystalline morphology, and crystal structure of PEPS was investigated in this research with the aim of increasing the crystallization rate. CNC enhanced both the melt crystallization behavior of PEPS during the cooling process and the overall crystallization rate during the isothermal crystallization process. The crystallization rate of PEPS became faster with an increase in CNC content. The crystalline morphology study directly confirmed the heterogeneous nucleating agent role of CNC. The crystal structure of PEPS remained unchanged in the composites. On the basis of the interfacial energy, the nucleation mechanism of PEPS in the composites was further discussed by taking into consideration the induction of CNC.

Effect of kaolin waste annealing on the structural and thermal behavior of poly(ε−caprolactone)

The heat treatment effect on kaolin waste from mining was evaluated on the structural and thermal behavior of poly(ε-caprolactone) (PCL). The PCL/KW (kaolin waste) and PCL/HTKW (heat-treated kaolin waste) composites were processed in an internal mixer and subsequently characterized by X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The kaolin waste showed kaolinite and quartz in its composition, while the heat treatment at 1200°C modified it to mullite, quartz and silica-rich amorphous phase. By XRD, there was an increase in the intensity of the peak 2θ = 23.9° of the PCL/KW composites compared to neat PCL. In contrast, PCL/HTKW composites tended to reduce the intensity of the peak 2θ = 23.9°, especially at 5% HTKW. The crystalline melting temperature and the degree of crystallinity of PCL/KW and PCL/HTKW composites were practically unchanged, compared to PCL. However, the crystallization process was more effective with the kaolin waste (KW) without heat treatment, indicating that the HTKW amorphous phase inhibited crystallization. The PCL/KW development promoted an increase in crystallization temperature, relative crystallinity, and crystallization rate, surpassing PCL and the PCL/HTKW system. In view of this, kaolin waste has the potential to accelerate the PCL crystallization process, contributing to add value to a material that would otherwise be discarded and minimizing environmental impacts.

The Synthesis of Biodegradable Poly(L-Lactic Acid)-Polyethylene Glycols Copolymer/Montmorillonite Nanocomposites and Analysis of the Crystallization Properties

This study makes use of polycondensation to produce poly (L-lactic acid)-(polyethylene glycols), a biodegradable copolymer, then puts it with organically modified montmorillonite (o-MMT) going through an intercalation process to produce a series of nanocomposites of PLLA-PEG/o-MMT. The exfoliation and intercalation of the montmorillonite-layered structure could be found through X-ray diffraction and transmission electron microscopy. The lower the molecular weight of poly (ethylene glycol), the more obvious the exfoliation and dispersion. The nanocomposites were investigated under non-isothermal crystallization and isothermal crystallization separately via differential scanning calorimetry (DSC). After the adding of o-MMT to PLLA-PEG copolymers, it was found that the PLLA-PEG nanocomposites crystallized slowly and the crystallization peak tended to become broader during the non-isothermal crystallization process. Furthermore, the thermal curve of the non-isothermal melt crystallization process of PLLA-PEG copolymers with different proportions of o-MMT showed that the melting point decreased gradually with the increase of o-MMT content. In the measurement of isothermal crystallization, increasing the o-MMT of the PLLA-PEG copolymers would increase the t1/2 (crystallization half time) for crystallization and decrease the value of ΔHc. However, the present study results suggest that adding o-MMT could affect the crystallization rate of PLLA-PEG copolymers. The o-MMT silicate layer was uniformly dispersed in the PLLA-PEG copolymers, forming a nucleating agent. The crystallization rate and the regularity of the crystals changed with the increase of the o-MMT content, which further affected the crystallization enthalpies.

Investigation of Crystallization and Relaxation Effects in Coarse-Grained Polyethylene Systems after Uniaxial Stretching

In this study, we investigate the thermo-mechanical relaxation and crystallization behavior of polyethylene using mesoscale molecular dynamics simulations. Our models specifically mimic constraints that occur in real-life polymer processing: After strong uniaxial stretching of the melt, we quench and release the polymer chains at different loading conditions. These conditions allow for free or hindered shrinkage, respectively. We present the shrinkage and swelling behavior as well as the crystallization kinetics over up to 600 ns simulation time. We are able to precisely evaluate how the interplay of chain length, temperature, local entanglements and orientation of chain segments influences crystallization and relaxation behavior. From our models, we determine the temperature dependent crystallization rate of polyethylene, including crystallization onset temperature.

The Casting Rate Impact on the Microstructure in Al–Mg–Si Alloy with Silicon Excess and Small Zr, Sc Additives

The study investigates the effect of casting speed on the solidification microstructure of the aluminum alloy Al0.3Mg1Si with and without the additions of zirconium and scandium. Casting was carried out in steel, copper, and water-cooled chill molds with a crystallization rate of 20 °C/s, 10 °C/s, and 30 °C/s, respectively. For each casting mode, the grain structure was investigated by optical microscopy and the intermetallic particles were investigated by scanning and transmission microscopy; in addition, measurements of the microhardness and the electrical conductivity were carried out. An increase in the solidification rate promotes grain refinement in both alloys. At the same time, the ingot cooling rate differently affects the number of intermetallic particles. In an alloy without scandium–zirconium additives, an increase in the ingot cooling rate leads to a decrease in the number of dispersoids due to an increase in the solubility of the alloying elements in a supersaturated solid solution. With the addition of scandium and zirconium, the amount of dispersoids increases slightly. This is because increasing the solubility of the alloying elements in a supersaturated solid solution is leveled by a growth of the number of grain boundaries, promoting the formation of particles of the (AlSi)3ScZr type, including those of the L12 type. In addition, the increase in the crystallization rate increases the number of primary nonequilibrium intermetallic particles which have a eutectic nature.

Dynamic crystallization behavior of PA-12/PP-MWCNT nanocomposites: non-isothermal kinetics approach

The effect of multi-walled carbon nanotubes (MWCNT) loading on the crystallization behavior of matrix polyamide 12 (PA-12), in PA-12/polypropylene-MWCNT (PP-MWCNT)-based nanocomposites were analyzed for their non-isothermal crystallization behavior at various cooling rates of 2.5–20 °C/min in differential scanning calorimetry (DSC). Several kinetic models such as Jeziorny (modified-Avrami), Mo and Tobin models were employed to analyze the crystallization behavioral trend with respect to time and temperature of the nanocomposites. The crystallization rate increased half-time of crystallization with MWCNT content as estimated from the Jeziorny theory. The linear agreement between Jeziorny model and experimental relative crystallinity outperforms the Tobin analysis where the coefficient of linear regression was found to be considerably trailing behind and off the satisfactory mark. The Mo model accounts for the percentage crystallinity and thereby successfully explained the crystallization behavior of PA-12 where the kinetic parameters increased with crystallinity indicating higher cooling rate for higher crystallinity. The MWCNT induced crystallization (nucleation activity) values were close to zero irrespective of MWCNT loading which reiterates the enhanced crystallization (rate) of PA-12 in the nanocomposites. Estimations based on Friedman approach showed inter-relationship between activation energy and crystallinity where the later was found to be governed by major (matrix) PA-12 phase.

Dependence of Crystallization Behavior of Interacting Telechelic Poly(butylene succinate) Oligomer on Molecular Weight

A large spherulite structure deteriorates the mechanical properties of crystalline polymers, and therefore various methods have been explored to increase primary nucleation density. Recently, chain-end modification has been proposed as an effective approach for regulating polymer crystal nucleation. However, the relevant nucleation mechanism still requires investigation. Therefore, in this work, 2-ureido-4[1H]-pyrimidinone (UPy) units, which can form stacks via quadruple hydrogen bonds with each other, are introduced as end groups for the preparation of interacting telechelic poly(butylene succinate) (PBS-UPy) oligomers with different molecular weights (Mns). The crystallization, especially the nucleation behavior of PBS-UPy, is studied in detail by comparing with the corresponding pre-polymer, the hydroxyl-terminal PBS (PBS-OH). The thermal properties of PBS-UPy exhibit similar Mn-dependent tendency to those of PBS-OH, but with weaker total crystallization rate. The spherulite growth rate is significantly reduced, whereas the primary nucleation density is highly promoted, after introducing UPy groups. Further investigation reveals that the mechanism of UPy stacks’ influence on nucleation ability changes from inhibition to promotion with respect to Mn. Even under an inhibition of nucleation ability, the final nucleation density is obviously increased because of a significant decline of the growth rate. In addition, the change in the impact of UPy stacks on nucleation ability is speculated to originate from the memory expression feasibility of ordered conformation in the melt during crystallization.

Enhanced Perovskite Solar Cell Performance by Adding Magnesium Acetate Using Two-Step Spin-Coating Method

The poor stability of perovskite materials is a problem of concern in commercialization. In this study, we investigated the doping of magnesium cations (Mg2+) in PbI2 to improve the stability and efficiency of perovskite solar cells. The doping effect of Mg2+ can increase the crystallization rate. The perovskite film fabricated structure consists of ITO/TiO2/perovskite/CuO. The fabrication method used is a two-stage spin coating. The concentrations of MgAc2 were used 0, 0.75, 1, and 1.25 mg ml−1. The characterizations used are XRD (X-Ray Diffraction), UV-Vis, SEM-EDX. While the performance of solar cells is measured using a solar simulator. The XRD pattern shows that the sample has a crystal structure of MAPbI3, PbI2, and CuO phases. The MAPbI3 lattice parameter increased with increasing Mg acetate concentration. The grain size of the perovskite layer is between 5 - 15 μm, with a thickness of about 30 μm. The efficiency of perovskite solar cells increases with the increasing concentration of MgAc2.

Investigation of Polyetherimide Melt-Extruded Fibers Modified by Carbon Nanoparticles

The fibers based on thermoplastic partially crystalline polyetherimide R-BAPB modified by vapor grown carbon nanofibers (VGCF) were prepared by melt extrusion, exposed to orientational drawing, and crystallized. All of the samples were examined by scanning electron microscopy, X-ray scattering, and differential scanning calorimetry to study how the carbon nanofiller influences on the internal structure and crystallization behavior of the obtained R-BAPB fibers. The mechanical properties of the composite R-BAPB fibers were also determined. It was found that VGCF nanoparticles introduced into R-BAPB polyimide can act as a nucleating agent that leads, in turn, to significant changes in the composite fibers morphology as well as thermal and mechanical characteristics. VGCF are able to improve an orientation degree of the R-BAPB macromolecules along the fiber direction, accelerate crystallization rate of the polymer, and enhance the fiber stability during crystallization process.