Crystallization,morphology, structure and thermal behaviour of nylon-6/rubber blends

An experimental study was carried out in order to investigate the morphological, kinetic, structural and thermodynamic properties of nylon-6/rubber (namely ethylene-propylene copolymer (EPM) and ethylene-propylene copolymer functionalized by inserting along its backbone succinic anhydride groups (EPM-g-SA)) blends. The morphology and the overall kinetics of crystallization of the blends strongly depend on the type of copolymer added to nylon and on the blend composition. The EPM-g-SA acts as a nucleating agent for the Ny spherulites and at the same time causes a drastic depression of the overall kinetic rate constant. This decrease is related to the increase of the melt viscosity observed in Ny/EPM-g-SA blends. The crystalline lamella thickness of the Ny phase in the blends is lower than that of pure Ny crystallized at the same T_c suggesting that the presence in the melt of an elastomeric phase disturbs the growth of the Ny crystals. The rubber does not influence the thermal behaviour of the nylon. The results found lead to the conclusion that in the melt nylon-6 is incompatible with both EPM and EPM-g-SA copolymers.     

Melting and crystallization behaviour of elastoplastic semicrystalline copolymers: poly(ether ester)

The melting and crystallization behaviour of an elastoplastic semi-crystalline poly(etherester) has been studied by differential scanning calorimetry. The shape of the melting endotherm is strongly dependent on heating rate and annealing time and results from the sum of simultaneous melting and crystallization phenomena. Samples prepared by different techniques, i.e. by solvent evaporation or by melt extrusion, behave very differently owing to specific crystal morphologies. By applying the Hoffman-Weeks plot, the equilibrium melting temperature has been extrapolated. The Avrami treatment allows the calculation of the index n and of the rate constant K from the isothermal kinetic data.     

Kinetic analysis of the crystallization of poly(p-phenylene sulphide)

Growth rates of spherulites were measured in poly(p-phenylene sulphide) crystallized from the melt and the quenched glass over the temperature range 100°C–280°C, possibly the most extensive overall range yet reported for any polymer and, as such, most propitious for study of régime III crystallization. For a medium M.wt. polymer, a régime II → III transition was obtained at 208°C using values of transport parameters common to many polymers ($\text{U1 = 1400}\text{cal mol}{}^{\mathrm{?1}}$, T_∞ ? T_g = 30°C) together with experimentally determined values of T⁰_m(315°C) and T_g(92°C). Under these conditions, the régime III/II slope ratio was found to be 2.07 (i.e. only 3.5% higher than predicted by régime theory), and reasonable estimates of surface free energies and of the work of chain folding were obtained. Other choices of the transport terms, including WLF and zero values, did not allow successful kinetic analyses. Although a régime I → II transition is predicted to occur at the high-temperature end of our growth-rate data, we found no experimental evidence for it. For a low M.wt. polymer, our analysis showed that régime III kinetics is obeyed at low temperatures, while at higher ones there is a continuous departure from that behaviour without, however, full attainment of régime II kinetics.     

Milk fat fractionation today: A review

Although anhydrous milk fat (AMF) has excellent properties, its variable physicochemical properties and its lack of functionality restrict its uses in the food industry. A technology involving dry fractionation of AMF has been developed, and its attributes include selectivity, reliability and general application. Combining two simple and reliable technologies,i.e., multi-step fractionation and blending, it is possible to overcome functionality problems and the seasonal variations of AMF. Lecture presented at the joint meeting of the International Society for Fat Research and the American Oil Chemists’ Society in Toronto, May 10, 1992.     

Phase transitions of canola oil sediment

Canola sediment was obtained from an industrial filter cake by solvent extraction. When heated in the differential scanning calorimeter (DSC) (5–100°C), the sediment exhibited a single narrow melting peak at around 74.8°C. No solid-state polymorphic transformation of the material could be detected over this temperature range. The X-ray powder diffraction pattern of canola sediment resembled waxes from other sources with an orthorhombic unit cell. The phase transition behavior of canola sediment in oil was studied by both DSC and polarizing microscopy. With increasing ratio of oil/sediment, a reduction in both melting temperature and transition enthalpy was observed. The shape of the supercooling curve resembled that of the melting curve. The induction time was determined by spectrophotometry and was used to calculate the interfacial free energyσ between sediment and oil; σ=4.71 erg/cm². The effect of temperature and sediment concentration on the clouding time of canola oil was studied; the clouding time was the shortest at 5°C.     

Polymorphism and solidification kinetics of the binary system POS-SOS

As a first approach to modeling the crystallization behavior of cocoa butter, the binary system of its two major components, 1-palmitoyl-2-oleoyl-3-stearoyl-s n-glycerol (POS) and 1,3-distearoyl-2-oleoyl-s n-glycerol (SOS), was studied. Differential scanning calorimetry, coupled with polarized light microscopy, was used to determine the phase diagrams of the various polymorphic forms (the most metastable sub-α and α, intermediate δ and β′, and stable β). Associated theoretical phase diagrams were also built. The presence of a solid solution for β and the ideal behavior of α were confirmed. Kinetics of isothermal solidification as a function of temperature were studied for three compositions of the POS-SOS system. Results were displayed as time-temperature-transformation (TTT) diagrams and crystal morphology maps. Dependence of the crystallization kinetics on composition of the binary system was interpreted in terms of nucleation and growth mechanisms. The asymmetry of the POS molecule induces a slower growth rate of the mixture when the concentration of this triacylglycerol is increased. Solidification kinetics during continuous cooling were studied at various cooling rates for the system POS-SOS 25:75. Experimental results were compared with numerical predictions of a solidification model based upon TTT data and an additivity principle. The calculated and measured volume fractions of the different phases formed and times of onset and finish of the solidification were in good agreement.     

A comparison of physical and chemical properties of milk fat fractions obtained by two processing technologies

Milk fat fractions from supercritical carbon dioxide (SC-CO₂) extraction were compared with commercial melt crystallization (MC) fractions for their physical and chemical properties. The fractions were analyzed for fatty acids, triacylglycerols, cholesterol, total carotenoid content, and volatile compounds. The fractions were also evaluated for solid fat content (SFC) by pulsed nuclear magnetic resonance and thermal profiles by differential scanning calorimeter (DSC). The distribution of fatty acids and triacylglycerols in the fractions depended on the fractionation technique used. SC-CO₂ separated fractions based on molecular weight rather than on melting point, which is the driving force for the MC process. The differences among the fractions were quantified from their SFC and DSC curves. Triacylglycerol profiles by high-performance liquid chromatography showed that the SC-CO₂ fractions were distinctly different from each other and from MC fractions. The SC-CO₂ solid fraction (super stearin) was the most unique. It had a high concentration of long-chain, unsaturated fatty acid-containing triacylglycerols in a narrow range of high molecular weight, indicating a homogeneity of this fraction that has not been attainable by other techniques. It was also enriched in β-carotene and was devoid of volatile compounds. As compared to liquid MC fractions, the liquid SC-CO₂ fraction had a high concentration of low-melting triacylglycerols and was enriched in volatile compounds. With SC-CO₂, it is thus possible to simultaneously fractionate and produce a flavor-rich concentrate at no extra processing cost.     

The influence of chemical interesterification on physicochemical properties of complex fat systems 1. Melting and crystallization

The effects of blending palm oil (PO) with soybean oil (SBO) and lard with canola oil, and subsequent chemical interesterification (CIE), on their melting and crystallization behavior were investigated. Lard underwent larger CIE-induced changes in triacylglycerol (TAG) composition than palm oil. Within 30 min to 1 h of CIE, changes in TAG profile appeared complete for both lard and PO. PO had a solid fat content (SFC) of ∼68% at 0°C, which diminished by ∼30% between 10 and 20°C. Dilution with SBO gradually lowered the initial SFC. CIE linearized the melting profile of all palm oil-soybean oil (POSBO) blends between 5 and 40°C. Lard SFC followed an entirely different trend. The melting behavior of lard and lard-canola oil (LCO) blends in the 0–40°C range was linear. CIE led to more abrupt melting for all LCO blends. Both systems displayed monotectic behavior. CIE increased the DP of POSBO blends with ≥80% PO in the blend and lowered that of blends with ≤70% PO. All CIE LCO blends had a slightly lower DP vis-à-vis their noninteresterified counterparts.     

动态熔融结晶工艺

浅谈动态熔融结晶特点及其工艺过程和工艺原理。