Crystallization Behavior of High Behenic Acid Stabilizers in Liquid Oil

The crystallization behavior and structure of mixtures of a high behenic acid stabilizer (HBS) in peanut oil, high oleic safflower oil and sesame oil were studied in order to elucidate the mechanism behind liquid oil stabilization. Both the chemical composition of the oil and cooling rate influenced the crystallization behavior and structure of HBS. The critical gelation concentration of HBS ranged from 6.5% for peanut oil crystallized at 3 °C/min to 11% for sesame oil mixtures crystallized at 0.6 °C/min. The free energy of nucleation (ΔG) was the highest for sesame oil (142 kJ/mol) followed by high oleic safflower oil (75.8 kJ/mol) and peanut oil (15.9 kJ/mol). The HBS peanut oil mixture displayed the highest storage modulus (G′) under both cooling rates studied. In general, HBS-oil mixtures crystallized at a higher cooling rate exhibited high SFC values, lower crystallization temperatures and a predominance of the β′ polymorph, and they had a microstructure characterized by uniformly sized spherulites. In contrast, slow cooling rates led to higher critical gelation concentrations of HBS, lower SFC, fractionation of higher melting and lower melting fractions, a more stable polymorphic form β and a wide range of spherulite sizes.     

Crystallization characteristics of hydrogenated canola oil as affected by addition of palm oil

Addition of palm oil at levels of 5, 10 and 15% to selectively and nonselectively hydrogenated canola oil increased the time of isothermal crystallization at 20°C and delayed the appearance of the isothermal crystallization peak as determined by DSC. The degree of supercooling was also increased. Addition of palm oil to canola oil before selective or nonselective hydrogenation decreased the time of the appearance of the isothermal crystallization peak. Rates of crystallization were determined in selectively hydrogenated canola palm oil mixtures which followed first order kinetics.     

Regulating the β′→β polymorphic transition in food fats

Hydrogenated cottonseed oil (HCSO) is commonly used as a β′-stable fat in margarines and shortenings. In the present study, the crystallization behavior of HCSO is altered via dilution, agitation, tempering regime, and the addition of an emulsifier [polyglycerol polyricinoleate (PgPr)]. Key properties assessed include crystal morphology (with polarized light microscopy), polymorphic behavior (with X-ray diffraction), and crystallization kinetics (with DSC). It is demonstrated that on considerable dilution with canola oil (4% w/w), HCSO can be crystallized in the β′ or β polymorph with associated changes in crystal morphology, depending on tempering regime. Crystallization from the melt to 25°C results in the β′-form, as there is insufficient supercooling to form the β polymorph but enough to form the metastable β′. With cooling from the melt to 5°C, there is adequate supercooling for the δ polymorph to form, with the presence of the canola oil facilitating the transformation toward this stable phase. Static vs. crystallization under agitation does not lead to visible changes in either polymorphic behavior or crystal morphology. However, there is extensive secondary nucleation and growth as a result of crystals breaking off accreting agglomerates. The presence of PgPr, added as a crystal modifier, does not affect the final crystal polymorph or morphology, except under one set of conditions—crystallization from the melt to 5°C with agitation, whereby it considerably alters crystallization behavior.     

Effects of Tripalmitin and Tristearin on Crystallization and Melting Behavior of Coconut Oil

We investigated the crystallization behavior of coconut oil (CO) with tripalmitin (PPP) and tristearin (StStSt) as additives. The effects of cooling rates (2°C, 5°C, and 10°C min⁻¹) and triacylglycerol concentrations (0.3–10 wt.%) on crystallization and melting behavior of CO were studied using differential scanning calorimetry (DSC) and optical microscopy. The polymorph was also examined using synchrotron radiation X-ray diffraction (SR-XRD). From the DSC results, two exothermic peaks for CO crystallization indicated two compositions in CO. From the SR-XRD results, the α form crystallized first at a high crystallization temperature (HTc) followed by β′ crystallization at low temperature (LTc), after which both HTc-α and LTc-β′ transformed into the β′ form of CO (CO-β′) solid solution during heating. Although the addition of PPP increased crystallization temperature of CO, it did not change its polymorphic pattern. However, during slow cooling with the StStSt additive, CO-β′ crystallization was induced from the melt directly. Moreover, under isothermal conditions, the crystallized StStSt spherulites induced nucleation of CO more than did PPP. Therefore, PPP increased the crystallization temperature of CO in both HTc and LTc fractions without changing the polymorph of CO, while StStSt promoted crystallization of CO directly into CO-β′.     

The formation of β‐polypropylene crystals in a compatibilized blend of isotactic polypropylene and polyamide‐6

Compatibilized polypropylene (PP)/polyamide (PA6) blends with and without β nucleating agent (β‐NA) are prepared, and are designated as Blend‐0.3 and Blend‐0, respectively. The melting and crystallization characteristic of the blends crystallized under different cooling rates and different crystallization temperatures are studied. It is observed that high β‐PP content can be developed in Blend‐0.3 only at slow cooling rates (<5°C/min), whereas high α‐PP content is formed at fast cooling rates. Isothermal crystallization analysis of Blend‐0 indicates that PA6 is an effective NA for α‐PP in the lower temperature range, whereas the α‐nucleating effect disappears in the higher temperature range. Blend‐0.3 can, therefore, be viewed as a system containing both α‐ and β‐NAs, simultaneously. PA6 is competing with β‐NA in inducing PP crystallization. Under the normal injection of Blend‐0.3, the melt will be cooled through the higher temperature that favors the effectiveness of β‐NA rapidly because of the faster cooling rate. However, the α‐nucleation effect from PA6 predominate at the lower temperature. This explains the difficulty in obtaining high β‐PP content in Blend‐0.3 from injection molding. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

Effect of processing conditions on physical properties of a milk fat model system: Microstructure

The effect of processing conditions on the microstructure of three blends of 30, 40, and 50% high-melting fraction [Mettler dropping point (MDP)=47.5°C] in the lowmelting fraction (MDP=16.5°C) of milk fat was studied. The effect of cooling and agitation rates, crystallization temperature, chemical composition of the blends, and storage time on crystalline microstructure (number, size, distribution, etc.) was investigated by confocal laser scanning microscopy (CLSM). To improve resolution, a mix of Nile blue and Nile red dyes was dissolved in the melted samples in proportions that did not modify the nucleation kinetics. Samples were then crystallized by cooling (0.2 or 5.5°C/min) to crystallization temperature (25, 27.5, and 30°C). After 2 h at crystallization temperature, a slurry was placed on a microscope slide and samples were stored 24 h at 10°C. During this period, more material crystallized. Slowly crystallized samples (0.2°C/min) formed different structures from rapidly crystallized samples (5.3°C/min). Crystals were sometimes diffuse and hard to distinguish from the liquid. Samples were darker as a result of this solid-mass distribution. However, rapidly crystallized samples had well-defined crystals and seemed to be separated by a distinct liquid phase. These crystals were not in touch with each other as was the case for slowly crystallized samples. Higher agitation rates led to smaller crystal size due to enhanced nucleation. Larger crystals were formed when crystallization occurred at higher temperatures. Storage time resulted in an increase of crystal size. Larger crystal size and structures with more evident links had a more elastic behavior with higher elastic modulus E’.     

Crystallinity of isothermally and nonisothermally crystallized poly(ether ether ketone) composites

PEEK/carbon fiber composites were prepared by a modified diaphragm forming machine under vacuum. The study of the degree of crystallinity versus the differential scanning calorimetry (DSC) heating rate indicated that 50°C/min was an optimal heating rate to suppress the reorganization of the specimens crystallized between 315°C and 255°C and to avoid superheating the specimens. A high volume of fibers constrained the spherulitic growth by an impingement mechanism, which depressed the crystallization rate and reduced the crystallinity. Thus the crystallization was still in process even after 240 min annealing at 300°C. The effect of the cooling rate on the degree of crystallinity was simulated and investigated in DSC at a heating rate of 50°C/min. The results indicated that the cooling rates ranging from 1°C/min to 100°C/min could be divided into five regions that were associated with a high volume of fiber and the crystallization regime. A Time-Temperature-Transformation diagram superposed on the Continuous-Cooling-Transformation curves allows us to predict the amount of crystallization in different regimes. The data points for the DSC method deviated from the prediction at the cooling rates above 60°C/min because of the recrystallization during DSC heating scans.     

Characterization of Enzymatically Interesterified Canola Oil and Fully-Hydrogenated Canola Oil Blends Under Supercritical CO2

Blends of canola oil and fully-hydrogenated canola oil (FHCO) containing 10, 30, and 50 wt% FHCO were interesterified enzymatically using Lipozyme TL IM (6 % of initial substrates, w/v) under supercritical CO₂ at 10 MPa and 65 °C for 2 h. Changes in polymorphic behavior and crystal morphology of non-interesterified initial blends (NIB) and purified enzymatically interesterified products (PEIP) were studied using X-ray diffraction spectroscopy (XRD) and polarized light microscopy. As well, the effects of blend ratio and enzymatic interesterification on rheological behavior were investigated. XRD analysis demonstrated the predominance of α form in FHCO while blending it with canola oil induced the formation of β form after crystallizing the samples at 24 and 5 °C for 12 h. Enzymatic interesterification caused the appearance of β′ forms and dramatically changed crystal morphology. The PEIP samples contained fewer crystal particles compared to NIB, but the crystals were more symmetrical. The elastic modulus (solid-like behavior) (G′) was lower in NIB with 30 wt% FHCO compared to the one with 50 wt% FHCO. Enzymatic interesterification also had a strong effect on G′ of the samples as it decreased after interesterification. The results of this study will help the development of conversion technologies under supercritical conditions in order to formulate more healthy fats having appropriate functional properties to address the industrial demand for the production of margarine and pastry shortenings.     

Effect of processing conditions on microstructure of milk fat fraction/sunflower oil blends

The effect of processing conditions on the crystallization of blends of a high-melting milk fat fraction and sunflower oil was investigated. Two cooling rates were selected for all studies: 0.1°C/min (slow rate) and 5.5°C/min (fast rate). Blends were crystallized in two conditions: (i) with agitation in an 80-mL crystallizer (dynamic), and (ii) on a microscope slide without agitation (static). The selected crystallization temperatures were 25, 30, and 35°C for both cooling rates. Photographs of the development of crystals with time were taken in both static and dynamic conditions, and the crystal size distribution was determined at the moment that the laser signal reached its peak. Photographs showed that when samples were cooled slowly, crystals had a more regular boundary, appeared to be more densely arranged, and were larger. In dynamic conditions, crystal sizes were smaller and the background contained numerous small crystals, which were not found in statically crystallized samples. All images showed that crystals were not single crystals, but grew by accretion.     

Effects of crystallization conditions on sedimentation in canola oil

The effects of various factors on sediment formation in canola oil were studied. The crystallization temperature of sediment varied with cooling rate, whereas the melting temperature depended on heating rate as well as the cooling rate during sediment formation. The final crystal size depended on cooling rate. The crystal habit of sediment was generally rod-like but could change to a round and leaf-like shape at low cooling rates (<0.5°C/min). Crystal nucleation occurred in the initial stage of crystallization, while crystal growth was observed during the whole crystallization process, decreasing as cooling proceeded. Crystal growth rate of the sediment was proportional to the crystal surface area Lecithin did not affect the phase transition temperatures of sediment, but retarded crystal growth.     

Polymorphism and Mixing Phase Behavior in Ternary Mixture Systems of SOS–SSO–OSO: Formation of Molecular Compound Crystals

This paper reports the phase behavior of ternary mixtures of saturated and cis‐monounsaturated mixed‐acid triacylglycerols (TAG) of SOS (1,3‐distearoyl‐2‐oleoyl‐glycerol), SSO (1,2‐distearoyl‐3‐oleoyl‐rac‐glycerol), and OSO (1,3‐dioleoyl‐2‐stearoyl‐glycerol) examined with X‐ray diffractometry and a differential scanning calorimeter. The ternary mixtures were crystallized by cooling from melt (60 °C) to 5 °C, and the crystals were then stabilized by storing the mixture samples at 28 °C for 10 days. The following results were obtained. (1) Molecular compound (MC) crystals of stable β polymorph having a double‐chain‐length structure (β‐2) were formed in mixtures of SOS/SSO/OSO in which the concentration of SOS was 50% with varying concentrations of SSO/OSO. This is in contrast to the fact that the stable polymorphic forms of the component TAG are β‐3 for SOS and OSO and β′‐3 for SSO. (2) When the concentration of SOS deviated from 50%, immiscible mixtures of β‐2 MC made of SOS/SSO/OSO and the component TAG (β‐3 of SOS and OSO and β′‐3 of SSO) were formed. Therefore, ternary mixtures of SOS/(SSO + OSO) = 50/50 with different concentrations of SSO and OSO are miscible mixtures of β‐2 of SOS/SSO and SOS/OSO.     

Effect of Tempering on the Texture and Polymorphic Behaviour of Margarine Fats

Separated fats from commercial soft (soft fat) and stick (stick fat) margarines and mixtures of hydrogenated super olein (H-olein) and canola oil, were temperature cycled between 4°C and 15,20 and 25°C. The polymorphic form, SFC and texture of the fats were evaluated. Temperature cycling of soft fats between 4 and 20°C resulted in the crystals being either in the β polymorphic form or mixtures of β′ and β. When temperature cycled between 4 and 15°C the presence of β′ crystals was improved, but there were soft fats that after the fourth cycle contained only β crystals. When stick fats were temperature cycled between 4 and 20°C, the crystals after the fourth cycle were either in the β′ form or contained mixtures of β′ and β. Mixtures of H-olein-canola showed superior β′ stability throughout. A mixture of 20% H-olein/canola oil compared well with the SFC and texture of soft margarines while a mixture of 40% H-olein/canola oil with those of stick margarines. Texture was evaluated by constant speed penetration. Texture of fats is very dependent on temperature history. DSC-crystallization curves of the fats showed a variety of patterns.     

Phase equilibrium and crystallization behavior of mixed lipid systems

As complex lipid systems, the phase and crystallization behavior of mixtures of a high-melting milk fat fraction with a low-melting milk fat fraction or canola oil was studied. A turbidity technique was developed to estimate solubility and metastability conditions of these lipid mixtures. Both solubility and metastability of the high-melting milk fat fraction in liquid lipids increased exponentially with temperature. At a given equilibration temperature, liquid phases and solid fractions with nearly identical melting profiles and TAG compositions were obtained regardless of the original concentration of the lipid mixture. The maximum melting temperature (MMT), as measured by DSC, of the liquid phase increased dramatically in the equilibrium temperature range of 27.5–35.0°C but did not change at temperatures below and above this range (down to 25.0°C and up to 40°C in this study). The content of long-chain TAG (C₄₆−C₅₂) increased and short-chain TAG (C₃₆−C₄₀) decreased in the liquid phases as the equilibrium temperature increased. A plot of the TAG group ratio (i.e, long-short-chain TAG) vs. equilibrium temperature was generated to illustrate the phase behavior of the complex lipid system and to represent a solubility curve, from which the supersaturation level for crystallization kinetics was determined. Higher supersaturation and lower temperature resulted in higher nucleation and crystallization rates. Compared to the system with a low-melting milk fat fraction, mixtures of the high-melting milk fat fraction with canola oil had higher nucleation and crystallization rates due to the lower solubility found for this system.     

Oil‐Fat Mixtures with Low Solid Fat Concentration: Influence of Fat Concentration and Cooling Conditions

Uniform suspension of particulates (salt or spices) in oil‐based marinades requires a gel behavior of the matrix. This can be achieved by adding a solid fat to the liquid oil. Besides rheology, appearance and thermal stability are important for the utilization as marinades. The influence of solid fat concentration (c_fat = 2.5–5.5 wt%) and average cooling speed (1.4, 2.6, and 4.7 °C/min) on the functional properties of oil‐fat gels from palm fat and canola oil was investigated. Oil‐fat mixtures showed complex physiochemical behavior depending on the solid fat concentration and cooling rate. All samples had a shear‐thinning behavior. Yield stresses and apparent viscosities increased at a constant cooling rate with increasing solid fat concentration. Frequency dependence of storage and loss modulus showed a transition from a viscous solution to a weak gel at c_fat > 3.5 wt%. Samples at increasing cooling rates transitioned to weak gels at lower fat concentration (2.5 wt%). Mixtures became turbid and increasingly whiter as both solid fat concentration and cooling rates increased, which was explained by increased light‐scattering by fat crystal aggregates. Results show the critical importance of proper formulation and preparation conditions on the functionality of oil‐based marinades.     

The Formation of a 12-Hydroxystearic Acid/Vegetable Oil Organogel Under Shear and Thermal Fields

External laminar oscillatory shear applied during crystallization in combination with different temperature fields was used to modify the microstructure and physical properties of edible oil organogels. Crystallization at a high cooling rate (30 °C/min) resulted in a spherulitic microstructure with a higher oil-binding capacity, lower storage modulus and lower yield stress compared with a material (with a fibrillar microstructure) crystallized at a slow cooling rate (1 °C/min). The application of an oscillatory shear resulted in the formation of novel microstructures depending on the cooling regime used. The application of an oscillatory shear (strain > 500 % and frequency = 1 Hz) resulted in the thickening of fibers observed in the slow-cooled material and an increased incidence of spherulite nucleation in the rapidly cooled material. Increasing the frequency of the oscillatory shear applied did not change the microstructure for the slow-cooled gel but further increased the incidence of nucleation for the rapidly cooled gel. The application of controlled-strain oscillatory shear to the crystallizing gel at either cooling rates resulted in an oily and very soft, paste-like material. This material had a lower storage modulus and poorer oil-binding capacity compared with the same gel crystallized statically. Reduction of the oscillatory strain from a maximum of 1500 to 500 % moderately mitigated the loss of mechanical properties and oil-binding capacity although these properties were in no way comparable to those obtained from static crystallization. The study shows that the application of oscillatory shear and different cooling regimes can be used to tailor a crystalline organogel. However, the application of continuous shear must be done with care as application of excessive shear can result in a complete breakdown in gel structure and large amounts of oil loss.     

Relationship between crystallization behavior, microstructure, and mechanical properties in a palm oil-based shortening

In this study, the effects of cooling rate, degree of supercooling, and storage time on the microstructure and rheological properties of a vegetable shortening composed of soybean and palm oils were examined. The solid fat content vs. temperature profile displayed two distinct regions: from 5 to 25°C, and from 25°C to the end of melt at 45–50°C. A peak melting temperature of 42.7°C was determined by DSC. Discontinuity in the crystallization induction time (determined by pulsed NMR) vs. temperature plot at 27°C also suggested the existence of two separate groups of crystallizing material. Isothermal crystallization kinetics were characterized using the Avrami and Fisher-Turnbull models. In using DSC and powder X-ray diffraction, the α polymorph formed upon fast cooling (>5°C/min), and the β′ form predominated at lower cooling rates (<1°C/min). An α to β′ transition took place upon storage. Fractal dimensions (D _f ) obtained by microscopy and image analysis showed no dependence on the degree of supercooling since D _f remained constant (∼1.89) at crystallization temperatures of 5, 22, and 27°C. Crystallization at 22°C at 1°C/min and 15°C/min yielded D _f values of 1.98 and 1.93, respectively. Differences in microstructure were observed, and changes in particle properties increased the parameter λ at higher degrees of supercooling.     

Influence of a novel β‐nucleating agent on the structure,morphology, and nonisothermal crystallization behavior of isotactic polypropylene

The crystalline structure, morphology, and nonisothermal crystallization behavior of isotactic polypropylene (iPP) with and without a novel rare earth‐containing β‐nucleating agent (WBG) were investigated with wide‐angle X‐ray diffraction, polar optical microscopy, and differential scanning calorimetry. WBG could induce the formation of the β form, and a higher proportion of the β form could be obtained by the combined effect of the optimum WBG concentration and a lower cooling rate. The content of the β form could reach more than 0.90 in a 0.08 wt % WBG nucleated sample at cooling rates lower than 5°C/min. Polar optical microscopy showed that WBG led to substantial changes in both the morphological development and crystallization process of iPP. At all the studied cooling rates, the temperature at which the maximum rate of crystallization occurred was increased by 8–11°C in the presence of the nucleating agent. An analysis of the nonisothermal crystallization kinetics also revealed that the introduction of WBG significantly shortened both the apparent incubation period for crystallization and the overall crystallization time. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Polymorphic stability of hydrogenated palm oleins in dilutions with unhydrogenated liquid oils

Palm oil was hydrogenated under selective and nonselective conditions. Some of the hydrogenated samples were chosen for their physical characteristics and were diluted with 70% sunflower oil. A commercial hydrogenated palm olein (H-olein) was diluted up to 80% with canola oil. The diluted mixtures were evaluated for their polymorphic β' stability by a temperature-cycling procedure between 4 and 20°C. All of the mixtures were stable in the β' form. The dropping point and solid fat content of the mixtures were compared with those of commercial soft and stick margarines. Soft margarines can be prepared from mixtures of 20% H-olein and 80% unhydrogenated oil, and stick margarines from 40% H-olein and 60% liquid oil. If canola oil is the liquid oil, the saturated content in the soft formulation is 13% and that of a stick formulation 17%.     

Polymorphic stability of hydrogenated canola oil as affected by addition of palm oil

Palm oil was added to canola oil before and after hydrogenation and the effect of this addition on the polymorphic stability of the hydrogenated oils was investigated. Palm oil was added to canola oil at two levels to produce hydrogenated canola and palm oil blends containing 5 and 10% palm oil. The levels of palm oil added to hydrogenated canola oil were 5, 10 and 15%. Samples were subjected to temperature cycling between 5 and 20°C as well as storage at 5°C up to 56 days. X-ray diffraction and polarized light microscopy were used to follow the changes of polymorphic form and crystal growth, respectively, during cycling and storage. Theβ-crystal contents of the oils were quantified based on the relative density of the characteristic short spacings using a Soft Laser Scanning Densitometer. The delaying effect of palm oil on phase transition was observed using Differential Scanning Calorimetry. Palm oil showed no effect on the polymorphic stability of the temperature cycled selectively hydrogenated oil, however, it delayed the transition rate at a constant temperature of 5°C. Addition of palm oil at the 10% level before hydrogenation and the level after hydrogenation proved to be effective in delaying polymorphic instability of nonselectively hydrogenated canola oil. Theβ′ stabilization effect of palm oil on the polymorphic stability of hydrogenated canola oil is most likely due to a decrease of fatty acid chain length uniformity.     

Crystallization Rates of Palm Oil and Modified Palm Oils

Differential scanning calorimetry and pulsed nuclear magnetic resonance were used in the estimation of crystallization kinetics of palm oil and modified palm oils. Differential scanning calorimetry was found to be more sensitive and could differentiate between crystallization during cooling and crystallization during isothermal conditions. Hydrogenated palm oils crystallized quickly and completely when cooled from 60° to 20°C, while palm oil and fractionated palm stearin continued to crystallize when held isothermally at 20°C.