Kinetics of Melt Crystallization of a Sunflower Oil‐Based Polyunsaturated Fatty Acid Mixture

Important parameters like supercooling and cooling rates affecting the melt crystallization of a polyunsaturated fatty acid (PUFA) mixture obtained from sunflower oil were investigated and compared via high‐resolution polarized‐light microscopy. PUFA was thermally characterized in a differential scanning calorimeter and the significant liquid‐solid‐phase transition temperatures determined were then implemented in the development of specific temperature profiles. Analyzed between two glass slides, induction times were found to decrease with low crystallization temperatures and the number of nuclei per unit area increased with higher supercooling and cooling rates. A comparison between the linear crystal growth rates of pure standards of each of the main fatty acids present in the PUFA mixture and the PUFA mixture itself indicated that the latter is much slower than that of each of its pure components.     

Isothermal Crystallization of Palm Oil-Based Fats with and without the Addition of Essential Oils

The objective of study was to evaluate the crystallization behavior of palm oil-based fats processed with and without the addition of essential oils (5% w/w) obtained from the flowers (EsOF) and stems (EsOS) of Pituranthos scoparius. Palm oil (PO) and a mixture of PO, soybean oil, and sunflower oil (Mix) were tested. The addition of the essential oils did not change the melting points of the fats but affected their crystallization behavior. A delay in crystallization was observed, evidenced by lower crystallization rates, and lower solid fat contents. This delay was comparable in the samples crystallized with EsOF and EsOS for the PO samples but EsOF was more efficient at delaying crystallization in the Mix sample. EsOF generated a less organized crystalline network in both samples (lower enthalpy values) while EsOS generated a more organized crystalline network (high enthalpy values) when used in the Mix sample. The addition of EsO also affected the crystal microstructure in some cases. While a slight increase in crystal size was observed for some PO samples crystallized with EsOF, no change or a decrease in crystal size was observed for the samples crystallized with EsOS. A slight decrease in crystal size was observed for Mix samples crystallized with EsOF while no effect was observed for these samples crystallized with EsOS. Results from this study show that these essential oils can be used as natural additives to modify the crystallization of fats for food applications and therefore widen their functional properties.     

Effect of the Addition of Waxes on the Crystallization Behavior of Anhydrous Milk Fat

Physicochemical characteristics of lipid-based foods depend, among other factors, on the microstructure and the characteristics of the lipid network formed during crystallization. The objective of this study, was to evaluate the effect of the addition of sunflower oil waxes on the crystallization and melting behavior of anhydrous milk fat (AMF), a lipid with a low content of palmitic and trans-fatty acids. The crystallization and melting behavior of AMF alone and with the addition of 0.25 and 0.5% of waxes was studied using a differential scanning calorimeter. The morphology of the crystallized samples was evaluated with a polarized light microscope. The addition of waxes induced and promoted the crystallization of AMF at high temperatures (>25 °C) as evidenced by lower induction times of crystallization and higher crystallization and melting enthalpies. In addition, smaller crystals and different morphologies were obtained when AMF was crystallized with the addition of waxes. These results suggest that waxes could be used as an additive to modify lipid networks and their physicochemical characteristics, such as texture, smoothness and mouthfeel.     

Effect of Milk Fat Concentration on Fat Crystallization of Palm Oil-Based Shortenings

The effect of different dosages of anhydrous milk fat (AMF) (25%, 50% and 75%, w/w) on shear-crystallization of fat blends made of refined palm oil, refined palm stearin, and rapeseed oil was studied. Classical techniques as differential scanning calorimetry (DSC), pulsed field gradient nuclear magnetic resonance (pfg-NMR), rheometer, and X-ray diffraction (XRD) were applied to evaluate the crystallization kinetics of fat blends as well as the fat compatibility between components in rapid cooling (15 °C min⁻¹), isothermal crystallization (at 15 °C), and storage (5 °C). Obtained results revealed that the mixtures of palm oils and milk fat had a low compatibility. The co-crystallization between triacylglycerols (TAG) of milk fat and of palm oil occurred during isothermal crystallization and storage resulting in slower crystallization kinetics and the formation of some eutectic mixtures.     

Effects of Ultrasonic Parameters on the Crystallization Behavior of Palm Oil

The crystallization behavior of palm oil (PO) without and with the application of high-intensity ultrasound (HIU) was investigated as the function of irradiation time (20, 60, 120, and 240 s), ultrasonic intensity (47.5, 95, 270, and 475 W) and temperature (20, 25, 30, and 36 °C). The effects on the crystallization behavior of PO were evaluated by ultraviolet/visible spectrophotometry, pulsed nuclear magnetic resonance and polarized light microscopy. Results indicated that all these parameters affected crystallization behavior. HIU significantly reduced the induction time and accelerated the crystallization rate at operating temperatures above 25 °C, but there was no significant difference at 20 °C due to high supercooling. The effects of HIU were more significant at higher power level and longer irradiation time, however, the thermal effect of ultrasound also increased with longer sonication time. The optimal sonication time was approximately 120 s which accelerated the crystallization rate of PO the most. The morphology studies suggested that HIU changed the growth mechanisms of crystals and generated smaller and uniformly crystals. At 36 °C, with extremely low supercooling condition, a combined effect was observed that prevented the separation of solid phase and liquid phase of the crystallized sample, and then led to a uniform distribution of crystals.     

Crystallization Enhancement by a High Behenic Acid Stabilizer in a Palm Oil-Based Model Fat Blend and its Corresponding Fat-Reduced Water-in-Oil Emulsion

A high behenic stabilizer (HBS) at concentrations of 0.3%, 0.6%, and 0.9% w/w was added to the oil phase of a fat-reduced water-in-oil (W/O) emulsion intended for margarine manufacture. The crystallization kinetics, thermal behavior, and microstructure of an oil phase and its 35/65 w/w fat-reduced W/O emulsion were studied. The oil phase was composed of a palm oil-based model fat blend, three emulsifiers, and the HBS. Differential scanning calorimetry results showed that, when 0.9% of stabilizer was added, the crystallization started 2.5 °C higher than when no HBS was added, hence reducing the time needed for crystallization. Polarized light microscopy results showed that the cocrystallization of the high-melting triacylglycerols of the oil phase with the HBS significantly decreased the fat crystal size and increased the number of crystals. The solid fat content also was increased by 2.4%. Interfacial tension experiments corroborated that HBS was located in the oil phase and not at the emulsion interface. This work shows that margarine can be successfully manufactured by adding 0.9% HBS to a 35/65 w/w fat-reduced W/O emulsion without losing functionality, as shown by the presence of the β′ polymorph. This work also suggests that 15% fat could be removed from the system without changing functionality by merely adding up to 0.9% of HBS.     

新型复合成核剂对PP/POE共混物结晶行为的影响

以低分子量聚酰胺6为主体制备了新型复合成核剂,采用高级流变仪、差示扫描量热仪、偏光显微镜等分析手段研究了几种成核剂对聚丙烯/乙烯-1-辛烯共聚物(PP/POE)共混物结晶温度、结晶形态及流变行为的影响。结果表明:新型复合成核剂均可以提高PP/POE共混物的结晶温度、结晶度和结晶速率,减小共混物的球晶尺寸,增加晶核密度,显著提高了PP/POE共混物的结晶性能。     

Crystallization Behavior of Fatty Acid Methyl Esters

Biodiesel from most agricultural feedstocks has flow properties that are prone to startup and operability problems during cold weather. Biodiesel from soybean oil is generally a mixture of long-chain fatty acid alkyl esters composed of 0.15–0.20 mass fraction saturated esters (melting point [MP] ≫ 0 °C) mixed with unsaturated esters (MP < 0 °C). This work investigates the crystallization properties of two saturated fatty acid methyl esters (FAME) commonly found in biodiesel from soybean oil. Differential scanning calorimetry (DSC) heating and cooling scans of methyl palmitate (MeC16), methyl stearate (MeC18) and methyl oleate (MeC18:1) in pure form were analyzed. Crystallization behavior in ternary FAME mixtures was inferred by the application of thermodynamic models based on ideal solution and freezing-point depression theories. Activity coefficients for MeC16 and MeC18 in MeC18:1 solvent were determined by analyzing DSC cooling curves for binary FAME mixtures. Eutectic points were predicted by both models. Crystallization onset temperatures inferred from freezing point depression theory were more accurate than those for ideal solutions with respect to a direct DSC cooling curve analysis of corresponding ternary mixtures. This work shows that the crystallization onset temperature (cloud point) of biodiesel may be predicted by freezing-point depression theory if the activity coefficients of the component FAME are known. The use of trade, firm, or corporation names in this publication is for the information and convenience of the reader. Such use does not constitute an official endorsement or approval by USDA or ARS of any product or service to the exclusion of others that may be suitable.     

Margarine-Like Emulsions Prepared with Coconut and Palm Oils: Analysis of Microstructure and Freeze–Thaw Stability by Differential Scanning Calorimetry

The objective was to study the microstructure and freeze–thaw stability of margarine-like emulsions formulated with vegetable fats using differential scanning calorimetry. Emulsions were prepared with 20% w/w dispersed aqueous phase and a continuous lipid phase composed by coconut oil (CO) and/or palm oil (PO) plus polyglycerol polyricinoleate (PGPR) as emulsifier. Mean temperature (T_M) and crystallization enthalpy (ΔH_c) were obtained from the exothermic peaks corresponding to freezing of aqueous phase. Successive cooling–heating–cooling cycles were applied to analyze changes in the exothermic peak. The emulsion prepared with CO (without PO) and 1% w/w PGPR in lipid phase showed higher water droplets size (T_M = −44.8 ± 0.1 °C) and lower quantity of stabilized aqueous phase (ΔH_c = 28.9 ± 1.2 J g⁻¹) prior to application of temperature cycles, while coalescence and (presumably) water transfer processes occurred during the treatment. The use of 2% w/w PGPR was sufficient to accomplish full stabilization of aqueous phase (T_M = −45.9 ± 0.1 °C; ΔH_c = 42.6 ± 0.3 J g⁻¹) before and after the freeze–thaw treatment. The total or partial (50%) substitution of CO by PO in emulsions with 1% w/w PGPR also improved the stability of the system, exhibiting slight microstructural changes. This enhanced stability would be linked to reduced water droplets size because of more rapid crystallization of lipid phase and immobilization of aqueous phase after emulsion preparation. In conclusion, it is possible to obtain margarine-like emulsions prepared with CO and/or PO using relatively low emulsifier concentration and maintaining a desired microstructure after freeze-thawing if the percentage ratio of both fats is controlled.     

Crystallization Kinetics of Coconut Oil in the Presence of Sorbitan Esters with Different Fatty Acid Moieties

Sorbitan esters (SEs) are shown to strongly influence the solidification kinetics and fat crystal morphology, but not polymorphic behaviour, of coconut oil (CNO). Solid‐state SEs (sorbitan monopalmitate, monostearate, and tristearate) affect both the high‐ and low‐melting fractions of CNO by decreasing induction time and by increasing crystallization rate as well as the number concentration of crystals. Liquid‐state SEs (sorbitan monoleate and trioleate) and canola oil do not specifically influence the high‐ or low‐melting fraction of CNO but do slow crystallization and lengthen induction time. The influence of sorbitan monolaurate, the only SE with an acyl group similar to that of CNO, is shown to depend on the crystallization temperature. At temperatures below its melting point, it only affects CNO's high‐melting fraction; at temperatures above its melting point, crystallization of both fractions is extensively decelerated. The lack of influence in polymorphic behaviour by any SE confirms no alteration of subcell arrangement, suggesting a lack of complementarity with the crystallizing fat. Overall, these SEs significantly impact the crystallization kinetics of CNO; however, this largely depends on type and concentration.     

复合成核剂对PP/POE共混体系等温结晶行为的影响

以低分子量尼龙6为主体制备了一种新型复合成核剂NF-10,采用差示扫描量热分析仪、偏光显微镜等分析手段研究了该成核剂对聚丙烯/乙烯-辛烯共聚物(PP/POE)共混体系结晶温度、结晶形态、等温结晶及其动力学的影响。结果表明:NF-10可以提高PP/POE体系的结晶温度、结晶度和结晶速率,减小体系结晶球晶的尺寸,提高晶核密度,显著改善PP/POE共混体系结晶性能。     

Crystallization and melting behaviors of poly(trimethylene terephthalate)

The crystallization and melting behaviors of poly(trimethylene terephthalate) (PTT) have been studied by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), and solid-state NMR. At certain crystallization temperatures (T_c) for a given time, the isothermally crystallized PTT exhibits two melting endotherms, which is similar to that of PET and PBT. At higher crystallization temperature (T_c = 210 °C), the low-temperature endotherm is related to the melting of the original crystals, while the high-temperature endotherm is associated with the melting of crystals recrystallized during the heating. The peak temperatures of these double-melting endotherms depend on crystallization temperature, crystallization time, and cooling rate from the melt as well as the subsequent heating rate. At a low cooling rate (0.2 °C/min) or a high heating rate (40 °C/min), these two endotherms tend to coalesce into a single endotherm, which is considered as complete melting without reorganization. WAXD results confirm that only one crystal structure exists in the PTT sample regardless of the crystallization conditions even with the appearance of double melting endotherms. The results of NMR reveal that the annealing treatment increases proton spin lattice relaxation time in the rotation frame, T_1ρ ^H, of the PTT. This phenomenon suggests that the mobility of the PTT molecules decreases after the annealing process. The equilibrium melting temperature (T _m ^o ) determined by the Hoffman-Weeks plot is 248 °C.     

Isothermal Curing Kinetics of Epoxidized Fatty Acid Methyl Esters and Triacylglycerols

Plant oil triacylglycerols are attractive renewable resources for biobased epoxy resins. We investigated the curing kinetics of three model epoxidized fatty acid methyl esters and representative epoxidized triacylglycerols with varied epoxide functionalities and distributions in the presence of a latent cationic initiator. Isothermal differential scanning calorimetry (DSC) was used to analyze the curing kinetics of the epoxy systems, and kinetic parameters (i.e., rate constants, reaction orders) were determined. Both epoxidized fatty esters and triacylglycerols followed the autocatalytic curing mechanism, and the DSC data were analyzed according to the Kamal autocatalytic model. Epoxidized methyl linoleate (EMLO) had the highest maximum curing rate, followed by epoxidized methyl linolenate (EMLON), and epoxidized methyl oleate (EMO) had the lowest maximum curing rate. We conclude that EMLO with two epoxide groups has the highest reactivity in this curing system, while the EMO with one epoxide group has the lowest reactivity. For epoxidized triacylglycerols, epoxidized camelina oil had the highest curing reactivity at higher temperatures, followed by epoxidized linseed oil and soybean oil.     

Comparative Oxidative Stability of Fatty Acid Alkyl Esters by Accelerated Methods

Several fatty acid alkyl esters were subjected to accelerated methods of oxidation, including EN 14112 (Rancimat method) and pressurized differential scanning calorimetry (PDSC). Structural trends elucidated from both methods that improved oxidative stability included decreasing the number of double bonds, introduction of trans as opposed to cis unsaturation, location of unsaturation closer to the ester head group, and elimination of hydroxyl groups. Also noticed with EN 14112 was an improvement in oxidative stability when a larger ester head group was utilized. Methyl esters that contained ten or less carbons in the fatty acid backbone were unacceptable for analysis at 110 °C (EN 14112) due to excessive sample evaporation. With respect to PDSC, a correlation was noticed in which the oxidation onset temperature (OT) of saturated fatty esters increased with decreasing molecular weight (R ² 0.7328). In the case of the monounsaturates, a very strong inverse correlation was detected between molecular weight and OT (R ² 0.9988), which was in agreement with EN 14112. Lastly, a strong direct correlation (R ² 0.8759) was elucidated between OT and oil stability index (OSI, EN 14112, 80 °C). The correlation was not as strong (R ² 0.5852) between OSI obtained at 110 °C and OT. Disclaimer: Product names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard of the product, and the use of the name by USDA implies no approval of the product to the exclusion of others that may also be suitable.     

Stability Assessment of Virgin Coconut Oil‐Based Emulsion Products

In recent years, there has been dramatic growth in the market for virgin coconut oil (VCO). VCO, a promising functional food oil, has gained popularity and captured public attention worldwide. Two VCO‐based emulsion products were developed as a new nutritional food supplement with the aim of increasing the consumption of VCO. The stability of VCO‐based emulsion products was assessed during a storage period of 3 months to gauge the quality of the optimized VCO‐based emulsions. The particle‐size distributions of the VCO‐based emulsions remained stable throughout the 3‐month storage period at 25 and at 50°C. However, a slight increase in the particle sizes was observed in the VCO‐based emulsions samples after 2 months of storage at 4 °C. Nevertheless, phase separation did not occur in either of the VCO‐based emulsions products throughout the storage‐stability assessment period. No signs of microbial growth were detected in the emulsion products during the storage period. Furthermore, no significant changes in the free fatty acid contents of the emulsion products were observed during storage at 4 or 25°C throughout the storage period. The VCO‐based emulsion products possessed sufficient emulsion stability to withstand changes at different storage temperatures.     

Effects of additives on non-isothermal crystallization kinetics and morphology of isotactic polypropylene

In this study, effects of commercial additives such as antioxidant and stabilizer on the non-isothermal crystallization kinetics of isotactic polypropylene without nucleating agents were investigated by differential scanning calorimetry (DSC) method. Kinetic parameters by Osawa, Avrami and Liu-Mo models and apparent activation energy of the crystallization by Kissinger model were calculated. A polarized optical microscope was also used to observe crystalline morphology of the polypropylene samples crystallized at different cooling rates. On the contrary rate inducing effects of the nucleating agents on the crystallization kinetics of the polypropylene, interestingly, it was found that such types of commercial additives reduced the overall crystallization rate of the polypropylene. Based on the crystallization kinetics and morphology of the samples, it was observed that commercial additives inhibit the chain diffusion toward the growing crystal faces thus slow the crystal growth rate. Furthermore, calculated nucleation activity (ϕ) for the additives showed that they do not act as effective nucleating agents. It was found that the crystallization activation energy of additive-free sample was higher than that of the sample which has commercial additives. Activation energies were found to be 233.6 and 276.7 kJ mol⁻¹ for the PP-1 and PP-2, respectively. Kinetic results also show importance of using of nucleating agents to increase the crystallization rate of polypropylene by increasing the nucleation and thus overall crystallization rate during polypropylene processing operations (esp. for a fast processing cycle in injection molding).     

Thermal Cyclization of 3‐Acyl‐4‐azidopyridines to Isoxazolo[4,3‐c]pyridines

4‐Azidopyridines such as 3‐acetyl‐4‐azido‐2‐pyridones 3 or 4‐azido‐3‐ethoxycarbonylpyridine 7 with reactive ortho‐acyl substituents were obtained from the 4‐hydroxy‐2‐pyridones 1 , resp. 5 via 4‐tosyloxy‐2‐pyridones 2 or the 2,4‐dichloropyridine 6 . DSC‐assisted thermolysis of the azides 3 and 7 resulted in electrocyclization and elimination of nitrogen to the isoxazolo[4,3‐c]pyridines 4 and 8 .     

Crystallization behavior of α‐cellulose short‐fiber reinforced poly(lactic acid) composites

The isothermal crystallization behavior of α‐cellulose short‐fiber reinforced poly(lactic acid) composites (PLA/α‐cellulose) was examined using a differential scanning calorimeter and a petrographic microscope. Incorporating a natural micro‐sized cellulose filler increased the spherulite growth rate of the PLA from 3.35 μm/min for neat PLA at 105°C to a maximum of 5.52 μm/min for the 4 wt % PLA/α‐cellulose composite at 105°C. In addition, the inclusion of α‐cellulose significantly increased the crystallinities of the PLA/α‐cellulose composites. The crystallinities for the PLA/α‐cellulose composites that crystallized at 125°C were 48–58%, higher than that of the neat PLA for ～13.5–37.2%. The Avrami exponent n values for the neat and PLA/α‐cellulose composites ranged from 2.50 to 2.81 and from 2.45 to 3.44, respectively, and the crystallization rates K of the PLA/α‐cellulose composites were higher than those of the neat PLA. The activation energies of crystallization for the PLA/α‐cellulose composites were higher than that of the neat PLA. The inclusion of α‐cellulose imparted more nucleating sites to the PLA polymer. Therefore, it was necessary to release additional energy and initiate molecular deposition. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013