Flow and crystallization of saturated fatty acid methyl esters and their binary mixtures

Demand for biodiesel has increased due to being a more environmentally-friendly fuel. Cold weather operation of biodiesel is challenging due to fatty acid methyl ester (FAME) content in biodiesel. Saturated FAMEs crystallize at relatively high temperatures, increase the viscosity of biodiesel, and can clog fuel lines. Here, several factors altered crystallization temperature (CT) of FAMEs, including composition, shear rate, and cooling rate. The crystallization of pure and binary mixtures of methyl palmitate, methyl myristate, and methyl stearate were studied under shear flow and static conditions. Static phase CTs of pure methyl palmitate, methyl myristate, and methyl stearate were 26, 14, and 35°C, respectively. In binary mixtures, CTs were depressed up to 7°C, which agreed with freezing point depression theory. Increasing shear rate up to 100 s⁻¹ decreased CT by 2°C compared to static conditions. Decreasing cooling rate from 1 to 0.1°C/min increased CT less than 2°C. Overall, FAME composition altered CT more than shear flow or cooling rate for pure and binary mixtures of three FAMEs.     

Anomalous behavior of unplasticized PVC compounds in capillary flow

Capillary rheometry was performed over a temperature range of 170°–200°C and a shear-rate range of 3–3000 sec^?1 on an unplasticized poly(vinyl chloride) compound. The data were corrected for the effect of pressure on viscosity, for pressure loss in the barrel and at the capillary entrance, and for the non-Newtonian velocity profile. The pressure coefficient of viscosity was found to be in the same order of magnitude as those previously found with linear polyethylene and butadieneacrylonitrile copolymers. The pressure–shear-rate superposition of the flow curves is valid at least approximately, although the temperature–shear-rate superposition is inapplicable. The shape of flow curves at 180°, 190°, and 200°C are concave downward when they are expressed as log-shear-stress-log-shear-rate. Similar plots at 170° and 175°C, however, are very different; shear stress is independent of shear rate at low shear rates, increases somewhat and becomes independent of shear rate again at high shear rates. There is no detectable temperature dependence of flow behavior at 170° and 175°C. Irregularly shaped extrudates were obtained at higher shear rates. At constant shear rate the irregularity increased with the length of the capillary. The effect of thermal-mechanical history on the particulate and crystalline structure is discussed with possible influence on the reproducibility of the rheological data.     

Effect of emulsion temperature on physical properties of palm oil-based margarine

Margarines made from refined, bleached, and deodorized palm oil at different emulsion temperatures showed no significant difference in their consistency, polymorphic behavior, and solid fat content (SFC) during storage, although differences were observed during processing. The emulsion temperatures studied were 40, 45, and 50°C, with other parameters such as emulsion flow rates, tube cooler temperature, and pin rotor speed kept constant. The SFC developed during processing and storage at 28°C was measured to evaluate the quality of margarine. The emulsion contained no SFC at any emulsion temperature studied. However, the amount of SFC in the perfector or tube cooler unit increased to 15.9, 13.9, and 15.6% in margarine produced at emulsion temperatures of 40, 45, and 50°C, respectively. At 40°C, the lowest SFC was developed during storage even though this margarine had the highest consistency. The softening point of this sample was moderately high and closely related to the type of crystal developed, which was a mixture of β′ and β crystals. Emulsion at 45°C gave the most stable margarine consistency and SFC with crystal in the β′ form even after the fourth week. At 50°C, moderately soft product was produced, which might be undesirable for some applications, although the crystals were in the β′ form.     

Effect of SBS Content on Low Temperature Impact Strength,Morphology and Rheology of PP-cp/SBS Blends

Izod impact strength of PP impact copolymer/Styrene-Butadiene-Styrene blends were evaluated at varied sub-zero temperatures and demonstrated 12 times enhancement in impact strength of 40% SBS containing blend over pure PP-cp at ?40°C. SBS content played a vital role in morphology development as it changes from droplet morphology to elongated ellipsoid to a seemingly networked structure leading towards different fracture mechanisms. Rheological properties of blends evaluated on capillary rheometer showed pseudoplastic behavior at varied shear rates (50 ? 10⁴ s^?1) at 220°C and good agreement between experimental shear viscosity and theoretical values as per log additivity principle at high shear rates.     

Melting behavior of blends of milk fat with hydrogenated coconut and cottonseed oils

The melting behavior of milk fat, hydrogenated coconut and cottonseed oils, and blends of these oils was examined by nuclear magnetic resonance (NMR) and differential scanning calorimetry (DSC). Solid fat profiles showed that the solid fat contents (SFC) of all blends were close to the weighted averages of the oil components at temperatures below 15°C. However, from 15 to 25°C, blends of milk fat with hydrogenated coconut oils exhibited SFC lower than those of the weighted averages of the oil components by up to 10% less solid fat. Also from 25 to 35°C, in blends of milk fat with hydrogenated cottonseed oils, the SFC were lower than the weighted averages of the original fats. DSC measurements gave higher SFC values than those by NMR. DSC analysis showed that the temperatures of crystallization peaks were lower than those of melting peaks for milk fat, hydrogenated coconut oil, and their blends, indicating that there was considerable hysteresis between the melting and cooling curves. The absence of strong eutectic effects in these blends suggested that blends of milk fat with these hydrogenated vegetable oils had compatible polymorphs in their solid phases. This allowed prediction of melting behavior of milk-fat blends with the above oils by simple arithmetic when the SFC of the individual oils and their interaction effects were considered.     

Residence time effects during capillary flow of a rigid PVC formulation

A typical rigid PVC formulation was rheologically characterized using capillary and parallel plate rheometers within regular processing temperatures and deformations. At 190°C and in an intermediate range of shear rates (10 to 100 l/s) the stress response was a function of the flowing time in the capillary. This behavior was not observed at other temperatures (170 and 210°C). Small amplitude oscillary shear experiments for the same compound but with various thermomechanical histories showed a different behavior as compared to the results of the capillary flow. The specific results of the capillary experiments are consistent with the hypothesis of particulate flow of PVC and also point out the influence of the stabilizers and lubricants in the flow behavior of the compound. The time dependent effect is analyzed in terms of the coupling of thermal and mechanical stresses with the unmelted particles present in the flow field.     

Flow behavior of polyacrylamide solution. III. Mathematical treatment

The flow behavior of polyacrylamide solutions was systematically determined over a wide range of temperatures (20–50°C) and concentrations (20–50 ppm) by using a coaxial cylinder viscometer. The results indicated that the rheological behavior of low-concentration polyacrylamide solution behaves similar to non-Newtonian fluids at all these concentrations. The effect of temperature on the consistency coefficient and flow behavior index of polyacrylamide solution of the different concentrations followed an Arrhenius-type relationship. Moreover, the effect of concentration on consistency coefficient and flow behavior index followed an exponential-law relationship at the temperatures used. The rheological constants for the Arrhenius and exponential-law models were determined. The combined effect of temperature and concentration on the coefficient of dynamic shear stress can be represented by a single equation: shear stress = 2.446 × 10⁻⁷exp(0.0639C + 3613/RT)(shear rate)^{2.337 exp(−0.00707C−245/RT)}. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2784–2789, 2001     

Thermal degradation of polypropylene in a capillary rheometer

Melt viscosity of a polypropylene (PP) resin was measured in a capillary rheometer between 220 and 260°C. The melt viscosity showed a power law behavior with strong shear rate dependence. The effects of temperature and shear rate on the degradation were studied in the rheometer by heating at 260 and 280°C, and extruding at shear rates up to 10000 sec ?1 . Melt flow index (MFI) of samples after shearing and heating treatment was measured to characterize the molecular weight change. An increase in MFI was found for PP sheared at high temperature. Heating for longer time also increased MFI. Increase of shear rate had a small effect on increasing MFI at 260°C but produced a larger effect at 280°C. A constant increment in MFI was observed in PP subjected to high temperature processing and was attributed to degradation due to oxygenated products.     

Characterization of the rheological behavior of UHMWPE gels using parallel plate rheometry

The effects of shear flow, temperature, and gel concentration on the rheological behavior of the ultrahigh-molecular-weight polyethylene (UHMWPE) gel in gel spinning process were investigated. The gel point was determined using parallel plate rheometry in rotation mode with controlled stress. Likewise, the flow curves at various temperatures were determined with controlled shear rate from 10⁻² to 10 s⁻¹. Whereas the shear storage modulus (G′) was obtained in oscillation mode with controlled strain from 1 to 100%. The result shows that the gel point of the UHMWPE gel increases with increasing gel concentration. The result from the strain sweep indicates that G′ of the gel is 1.5 × 10³ Pa, and it exhibits a plateau at low strain, but it is reduced with increasing strain. At low shear rates, for temperatures above gel point, all flow curves exhibit a plateau, then go down with increasing shear rate. Studying contributions from UHMWPE gel concentration, temperature, and shear rate for rheological view, we found that spinning at 6% UHMWPE (MW : 1.4 × 10⁶ g/mol) gel and 140°C gives the best effect on formation of fiber structure. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 1009–1016, 1998     

Temperature and concentration dependent effect of partial glycerides on milk fat crystallization

Two diglycerides (distearin and diolein) and two monoglycerides (monostearin and monoolein) were added to milk fat in a concentration of 0.5% and 1%. The isothermal crystallization behavior was evaluated at 22 °C, 23.5 °C, 25 °C and 26.5 °C by DSC and pNMR. The crystallization kinetic was quantified by means of two models. It was noticed that the effect of the minor components on the crystallization behavior depends on temperature and concentration. The type of esterified fatty acids and the polar head of the amphiphilic molecule determine to what extent partial glycerides influence the nucleation and crystal growth of triglycerides. Moreover the degree of insolubility of partial glycerides in the melt determines which effect (on growth or on nucleation) predominates. Stearic acid based partial glycerides enhance nucleation at low temperatures, while at higher temperatures an interaction with the crystal growth predominates. Oleic acid based partial glycerides have an effect on the nucleation process while no interaction with the crystal growth was observed.     

Capillary extrusion of elastomeric emulsion crosslinked interpenetrating networks

The rheological properties of an elastomeric emulsion thermosetting (EMSET) interpenetrating network (IPN) of poly(ethyl acrylate) (70 percent) and polystyrene (30 percent) were studied using a capillary rheometer to test if the submicron thermoset particles, persumably the flow units, could flow as a thermoplastic matrix. The IPN exhibited power law behavior over a wide range of shear rates (0.05 to 500 s^?1), with a power law exponent of approximately 0.18 over a large range of temperatures (80 to 200°C), without a yield stress or a Newtonian plateau evident. The flow activation energies were found to be comparable with most processable thermoplastic materials at 4 kcal/mole for constant shear rates, and 20 kcal/ mole for constant shear stresses. The effect of a roll mill shear modification step prior to extrusion indicated stability of the flow units. The pervasive rippling melt fracture and the significant slip velocity at the wall emphasized the importance of slip in the flow mechanism of this elastomeric EMSET IPN.     

Shear and Rapeseed Oil Addition Affect the Crystal Polymorphic Behavior of Milk Fat

The effect of shear on the crystallization kinetics of anhydrous milk fat (AMF) and blends with 20 and 30 % w/w added rapeseed oil (RO) was studied. Pulse ¹H NMR was used to follow the α to β′ polymorphic transition. The NMR method was confirmed and supported by SAXS/WAXS experiments. Samples were crystallized at 5 °C and shear of 0, 74 or 444 s^?1 was applied during early crystallization, in the NMR tube. High shear rates decreased the amount of α polymorph formed and accelerated the polymorphic transition; however, shear did not affect the final solid fat content (SFC). The α to β′ transition occurred faster in the presence of RO allowing more room for the conformational changes to occur. Final SFC decreased with increasing RO content. Shear applied in 20 and 30 % blends caused the destruction of β′‐related 3L structure leaving only 2L packing. In AMF and statically crystallized samples, both 3L and 2L packing existed. Shear did not affect the amount of β crystals formed. The study shows that both shear and RO affect the polymorphic behavior of milk fat, and that ¹H NMR is able to detect polymorphic transition in blends with up to 30 % w/w RO.     

Effect of CO2 Bubbles on Crystallization Behavior of Anhydrous Milk Fat

A study was designed to observe the effect of bubbles created from dissolved CO₂ (0–2000 ppm) on crystallization and melting behavior, fat polymorphs, microstructure, and hardness of anhydrous milk fat (AMF) under nonisothermal crystallization conditions. Calculated amounts of dry ice were added to generate 2000 ppm CO₂ at low partial pressure, and an ultrasound (205 kHz, 10 s; US) treatment was delivered at 35 °C through a noncontact metal transducer on the molten AMF to generate bubbles (~500 nm) of CO₂. The generated CO₂ bubbles were found to induce a higher onset of crystallization temperature during cooling from 35 to 5°C at the rate of 0.5°C min⁻¹. The changes in crystallization behavior owing to the generation of a smaller and significant number of TAG crystals also increased the hardness of the AMF at room temperature and refrigerated conditions. The work suggested the potential use of CO₂ nanobubbles derived from the dry ice with the emission of low power US to control the crystallization behavior and thereby the physical properties of milk fat-containing dairy products.     

Retardation of Crystallization through the Addition of Dairy Phospholipids

The objective of this work was to identify the effects that milk phospholipids (PL) have on crystallization of anhydrous milk fat (AMF). Three mixtures were prepared by adding 0%, 0.01%, and 0.1% PL to AMF. Each mixture was crystallized for 90 min at 24, 26, and 28 °C. The solid fat content was measured as a function of time and fitted to the Avrami equation. Melting point, thermal behavior, viscoelastic properties, and crystal morphology were all measured at 90 min. All assays were repeated, as well as hardness, after being stored at 5 °C for 48 hours. Samples containing PL showed slower crystallization as concentration increased especially at higher temperatures (26 and 28 °C). The addition of PL caused a difference in crystal morphology resulting in visibly larger crystals at 90 min. The elasticity and hardness at 90 min were influenced by the addition of PL at 24 °C with lower values obtained in samples with PL compared to the AMF alone. No differences in hardness nor in elasticity was observed for samples crystallized at 26 and 28 °C. A decrease in melting enthalpy was observed in samples with PL indicating a reduction in crystallization at all temperatures, which was supported by crystal morphology.     

Rheological properties of new polymer compositions for sand consolidation and water shutoff in oil wells

The rheological properties of some newly developed polymer compositions have been investigated with and without crosslinking. These polymer compositions were developed as a water shutoff and sand consolidation treatment agents for producing oil and gas wells. The effects of several variables on the rheology of the compositions were evaluated over a wide range of temperatures (25–110°C), shear rates (0–500 s^?1), brine percentages (0–15%), crosslinker types and concentrations (0–3%), and polymer concentrations (6–50%). It was found that increasing the shear rate from 0 s^?1 to 100 s^?1 caused shear thinning and reduction of the viscosity of the dilute solutions (6–13%) from 25 cP to ～ 3 cP at 80°C. In contrast, for the concentrated solutions (20–50%), the viscosity dropped slightly in the shear rate range 0–10 s^?1, and subsequently decreased more slowly up to shear rates of 500 s^?1. The viscosities of all polymer solutions dropped by a factor of 2 as the brine concentration increased from 0% to 15%. Finally, aging time coupled with shear rates and higher percentages of crosslinkers accelerate the buildup of viscosity and gelation time of the polymer compositions. For concentrated solutions, shear rates ranging within 0–200 s^?1 accelerated gelation time from 9.75 h to 2–3 h, when they were sheared at 80°C. The polymeric solutions exhibited Newtonian, shear‐thinning (pseudo‐plastic), and shear‐thickening (dilatant) behavior, depending on the concentration, shear rate, and other constituents. In most cases, the rheological behavior could be described by the power law. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Viscosimetric Investigation of Plasticized Epoxy Resin

Blends of diglycidyl ether of bisphenol-A epoxy resin and adipic acid, ethylene glycol, diethylene glycol polyester copolymer have been studied regarding viscosity behavior. Both the rheological measurements carried out on the molten mixtures over a large interval of shear rates and the intrinsic viscosity of the blend solutions pointed to an immiscibility at temperatures ranging from 30° to 90°C. The rheological parameters evaluated on the flow of the mixtures against temperature and the shear rate led to the conclusion that the tested blends have a non-Newtonian rheological behavior of the pseudoplastic type.     

In Situ Rheo-NMR Measurements of Solid Fat Content

The properties of crystallized fats depend on their solid fat content (SFC) and their fractal structures. The SFC and the structures are dramatically affected during crystallization under shear flow. A mini-Couette cell was developed to crystallize fat samples under shear. The cell was tested with blends of canola stearin (CS) in canola oil (CO) in a 20-MHz NMR spectrometer. The blends were placed in the cell, melted at 80 °C, and then crystallized under different shear rates (58–460 s⁻¹) at 40 °C inside the spectrometer for 4 h. Time averaged NMR free induction decay (FID) curves were captured at 20 s intervals. SFC values were calculated using parameters determined by a calibration procedure. The SFC values determined by the direct method with and without the shaft of the Couette device were reasonably close. Similar results were observed with and without shear in the Couette device. The FID curves did not show a significant difference either. Therefore this system is accurate for in-situ time-resolved determination of SFC under shear flow. Furthermore, a combination of the direct and the indirect methods was successfully used to estimate the temperature increase due to viscous heating. The system developed will help in understanding the effects of shear flow on SFC of nanostructured lipid multicomponent systems. This will permit the optimization of the manufacturing processes.     

Decaffeination of guaraná seeds in a microextraction column using water-saturated CO2

Experimental data on the reduction of the caffeine content of guaraná seeds with water-saturated supercritical carbon dioxide were obtained in order to provide information on the ability of supercritical fluids for the decaffeination of widely consumed caffeine-rich natural products. The extraction was performed using a semi-continuous flow high-pressure micro-extraction apparatus at 40 and 70 °C and pressures of 100, 200 and 400 bar. Carbon dioxide flow rates of 5.7 and 9.4 g min⁻¹ were used. The extraction curves obtained showed the existence of thermodynamic solubility dependent, intermediate and diffusion controlled regions. Extraction at 400 bar and 70 °C using water-saturated supercritical carbon dioxide at a flow rate of 5.7 g min⁻¹ allowed the removal of almost 98% of the initial caffeine content in wet ground guaraná seeds, in a period of 240 min. When extractions were performed at lower pressures or temperatures, additional time and larger amounts of carbon dioxide were necessary to achieve the same yield. Increasing carbon dioxide flow rate did not present any economic advantage unless the extraction was limited to the thermodynamic solubility region. For total extraction of caffeine, the use of low flow rates resulted in a similar final product yield but at a much lower solvent consumption. A retrograde behavior for the extraction of caffeine from guaraná seeds was also observed at 100 bar for the 40 and 70 °C isotherms.     

PRODUCTION OF BIOFUEL FROM SOFT SHELL OF PISTACHIO (PISTACIA VERA L.)

Soft shell of pistachio (Pistacia vera L.) pyrolysis experiments were performed in a fixed-bed reactor to produce bio-oil. The effects of temperature, heating rate, and sweep gas (N₂) flow rates on the yields and compositions of products were investigated. Pyrolysis runs were performed using reactor temperatures between 350° and 500°C with heating rates of 15° and 50°C/min. Nitrogen flow rates varied between 50 and 200 cm³/min and mean particle size was 0.8 mm. The maximum bio-oil yield of 33.18% was obtained in a nitrogen atmosphere with nitrogen flow rate of 150 cm³/min and at 450°C pyrolysis temperature with a heating rate of 50°C/min.The elemental analysis and gross heating value of the bio-oil were determined, and then the chemical composition of the bio-oil was investigated using chromatographic and spectroscopic techniques. The chemical characterization has shown that the bio-oil obtained from soft shell of pistachio can be used as a renewable fuel and chemical feedstock.     

Studies on fiber formation of thermotropic copolyesters

Thermotropic copolyesters PET/60 PHB and PET/80 PHB fibers are melt spun at different extrusion temperatures and at different draw-down ratios. The flow behavior of PET/60 PHB is studied at different temperatures and shear rates. The melt of (PET/60 PHB) at temperatures above 265°C exhibit low viscosity and low activation energy of flow. The modulus and strength for both PET/60 PHB and PET/80 PHB fibers increase with the increase in extrusion temperature and draw-down ratio in the ranges studied. High birefringence, indicating the presence of mesophase is observed between 265 and 300°C on a hot stage polarizing microscope. X-ray diffraction patterns show that the molecular orientation increased with increasing draw-down ratio. Scanning electron microscopy of these fibers shows a well-developed highly oriented fibrillar structure. Superior mechanical performance of fibers spun at around 275°C are attributed to the presence of nematic mesophase in the polymer melt. © 1993 John Wiley & Sons, Inc.