Crystallization behavior of milk fat,palm oil,palm kernel oil,and cocoa butter with and without the addition of cannabidiol

The objective of this study was to evaluate the effect of cannabidiol (CBD) on the crystallization behavior and physical properties of various fats. Anhydrous milk fat (AMF), palm oil (PO), palm kernel oil (PKO), and cocoa butter (CB) were chosen for this study, for their unique crystallization behaviors. CBD was added at 1 and 2.5% wt/wt to these fats, and the crystallization behavior was evaluated at 26°C for AMF and PO and at 22°C for PKO and CB. Control samples with no CBD were prepared and evaluated as well. Results show that CBD delayed the crystallization of all fats with the least effect observed for the PO. Slight increases in crystal size were observed with the addition of CBD for all samples. CBD did not affect the melting profile of AMF or CB, but it increased the peak temperature of PO and decreased the enthalpy of PKO. Similarly, hardness was only affected by CBD in PO samples, with harder materials obtained for samples containing 2.5% CBD. The same trend was observed for elasticity. In addition, the elasticity of AMF increased with the addition of CBD but not its hardness. Overall, this study indicates that the effect of CBD on fat crystallization is highly dependent on the type of fat used. Producers of fat-based products that are willing to include CBD in their formulations must carefully control processing conditions to ensure product quality.     

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 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’.     

Potential Effect of Cavitation on the Physical Properties of Interesterified Soybean Oil Using High-Intensity Ultrasound: A Long-Term Storage Study

The objective of this research was to evaluate if cavitation events generated during sonication (20 kHz, 216 μm amplitude, 10 s) are responsible for changes in physical properties of a fat with low levels of saturated fatty acids and if these changes are maintained during storage. The fat was crystallized at 24 and 34 °C and stored at 25 °C for up to 24 weeks. An increase in solid fat content and melting enthalpy was observed for sonicated samples crystallized at 34 °C and an increase in elasticity was observed for sonicated samples crystallized at 24 °C (P < 0.05). Hardness increased in sonicated samples crystallized at 24 and 34 °C (P < 0.05) after 60 min of crystallization and after 24 weeks storage. Elasticity of non-sonicated samples crystallized at 24 °C decreased (P < 0.05) after storage at 25 °C for 48 h while it remained constant in sonicated samples. Sonicated samples had more, and smaller crystals compared to the non-sonicated ones. No significant change was observed in physical properties of sonicated samples crystallized at 24 °C and 34 °C during the 24 weeks of storage. Sonication at 24 °C was less efficient at changing the physical properties of the fat compared to 34 °C; however, the number of subharmonic components generated during sonication at these two temperatures was not affected by crystallization temperature. These results suggest that changes in physical properties are associated with secondary effects of sonication such as bubble streamers rather than changes in cluster dynamics.     

Effect of Lactose Monolaurate and High Intensity Ultrasound on Crystallization Behavior of Anhydrous Milk Fat

Crystallization behavior of anhydrous milk fat (AMF) was studied with the addition of 0.025 and 0.05 % lactose monolaurate (LML). The crystallization behavior was studied at low (ΔT = 3 °C) and high supercooling (ΔT = 6 °C). Polarized light microscopy and laser turbidimetry indicated a delay in crystallization on addition of 0.025 % and 0.05 % LML or Tween 20 to AMF. High intensity ultrasound (HIU) was applied to AMF samples with 0.05 % LML and lower supercooling (T _c = 31 °C; ΔT = 3 °C). HIU application in AMF and AMF + 0.05 % LML induced crystallization (p < 0.05) changing the induction time (τ) at 31 °C from 34.20 ± 1.67 min (AMF) and 47.07 ± 1.27 min (AMF + 0.05 % LML) to 23.23 ± 3.26 min (AMF) and 25.00 ± 0.87 min (AMF + 0.05 % LML). Melting enthalpies (ΔH) of AMF were significantly higher (p < 0.05) than the ones observed for AMF + 0.05 % LML when crystallized without HIU, while enthalpy values increased significantly in AMF + 0.05 % LML samples when crystallized with HIU reaching similar values to the ones obtained for AMF without LML. The viscosity of AMF significantly decreased (p < 0.05) on addition of 0.05 % LML and significantly increased on HIU application.     

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.     

The effect of minor components on milk fat crystallization

Milk fat is composed of 97–98% triacylglycerols and 2–3% minor polar lipids. In this study triacylglycerols were chromatographically separated from minor components. Isolated diacylglycerols from the polar fraction were also added back to the milk fat triacylglycerols. The crystallization behaviors of native anhydrous milk fat (AMF), milk fat triacylglycerols (MF-TAG), and milk fat triacylglycerols with diacylglycerols added back (MF-DAG) were studied. Removal of minor components and addition of diacylglycerols had no effect on dropping points or equilibrium solid fat contents. Presence of the minor components, however, did delay the onset of crystallization at low degrees of supercooling. Crystallization kinetics were quantified using the Avrami model. Sharp changes in the values of the Avrami constant k and exponent n were observed for all three fats around 20.0°C. Increases in n around 20.0°C indicated a change from one-dimensional to multidimensional growth. Differences in k and n of MF-DAG from AMF and MF-TAG suggested that the presence of milk fat diacylglycerols changes the crystal growth mechanism. Apparent free energies of nucleation (ΔG_c,apparent) were determined using the Fisher-Turnbull model. (ΔG_c,apparent) for AMF was significantly greater than ΔG_c,apparent for MF-TAG, and ΔG_c,apparent for MF-DAG was significantly less than those for both AMF and MF-TAG. The microstructural networks of AMF, MF-TAG, and MF-DAG, however, were similar at both 5.0 and 25.0°C, and all three fats crystallized into the typical β′-2 polymorph. Differential scanning calorimetry in both the crystallization and melting modes revealed no differences between the heat flow properties of AMF, MF-TAG, and MF-DAG.     

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.     

Sonocrystallization of Interesterified Soybean Oil With and Without Agitation

Interesterified soybean oil was crystallized at 29, 34, and 35 °C with and without the use of high‐intensity ultrasound. Samples were crystallized using either (1) continued agitation for the entire crystallization process (CA) or (2) agitation for 10 min (A10) followed by static crystallization. Sonication and agitation decreased the induction period of nucleation at higher temperatures and changed the crystal morphology, crystallization kinetics, and viscoelasticity of the sample. Sonication reduced the crystal sizes and significantly (P <0.05) increased the viscosity (5.2 ± 1.2 to 2369.6 ± 712.1 Pa s) and elastic modulus (83.2 ± 4.1 to 69,236.7 ± 26,765 Pa) of the crystalline networks obtained at 29 °C under A10 condition. An increase in viscosity and elasticity was also observed for sonicated samples crystallized at 34 and 35 °C under A10 and all CA conditions but these differences were not statistically significant (P >0.05). Sonication increased crystallization rates for all conditions tested. Kinetic constants obtained from an Avrami fit increased from1.3 × 10^?5 to 6.8 × 10^?5 min^?n for samples crystallized at 29 °C A10 without and with sonication, respectively, and from 2.6 × 10^?9 to 2.4 × 10^?7 min^?n for samples crystallized at 34 °C A10 without and with sonication, respectively. This increase in the crystallization rate was also observed for samples crystallized under the CA condition at 29 °C.     

Tempering method for chocolate containing milk-fat fractions

Anhydrous milk fat (AMF) was fractionated by a two-stage dry fractionation process to produce three fractions—high-(HMF), middle-(MMF), and low-melting (LMF). The effect of replacing 12.2–40% by weight of cocoa butter with these fractions on the tempering profile of milk chocolate was studied. Degree of temper was evaluated by differential scanning calorimetry, and expressed as the ratio of enthalpies of melting for higher-stability polymorphs to those of lesser stability. The degree of temper was dependent on the crystallization time and temperature, and the type and quantity of milk-fat fraction in the formulation. Chocolates containing AMF or its fractions in concentrations of up to 20 wt% (total fat basis) were tempered after a conventional thermocycling tempering process (50°C/30 min, 27.7°C/4 min, 31°C/2 min) to obtain products with good contraction and mold release properties. For those milk chocolate formulations that did not temper by the conventional method and resulted in poor contraction and mold release, a new tempering protocol was developed. Lower crystallization temperatures and/or longer holding times were required at concentrations of AMF, MMF, or LMF above 20%. Chocolate containing HMF required slightly higher crystallization temperatures because of high viscosity. Chocolates containing up to 35% HMF and up to 40% of the total weight of fat in the chocolate of AMF, MMF, and LMF were successfully tempered by adjusting crystallization time and temperature.     

Effect of processing conditions on crystallization kinetics of a milk fat model system

Crystallization behavior of three blends of 30, 40, and 50% of high-melting fraction (MDP=47.5°C) in low-melting fraction (MDP=16.5°C) of milk fat was studied under dynamic conditions in laboratory scale. The effect of cooling and agitation rates, crystallization temperature, and chemical composition of the blends on the morphology, crystal size distribution, crystal thermal behavior, polymorphism, and crystalline chemical composition was investigated by light microscopy, differential scanning calorimetry (DSC), X-ray diffraction (XRD) and gas chromatography (GC). Different nucleation and growth behavior were found for different cooling rates. At slow cooling rate, larger crystals were formed, whereas at fast cooling rate, smaller crystals appeared together. Slowly crystallized samples had a broader distribution of crystal size. Crystallization temperatures had a similar effect as cooling rate. At higher crystallization temperatures, larger crystals and a broader crystal size distribution were found. Agitation rate had a marked effect on crystal size. Higher agitation rates lead to smaller crystal size. Cooling rate was the most influential parameter in crystal thermal behavior and composition. Slowly crystallized samples showed a broader melting diagram and an enrichment of long-chain triacylglycerols. Crystallization behavior was more related to processing conditions than to chemical composition of blends.     

Relationship between oil binding capacity and physical properties of interesterified soybean oil

The objective of this study was to identify the physical properties of an interesterified soybean oil (EIESOY), containing 45% saturated fatty acids (SFA), that correlates with high oil binding capacity (OBC) and low oil loss (OL). In this study, three EIESOY samples were analyzed; a 100% sample, a 50% sample diluted with 50% soybean oil, and a 20% sample diluted with 80% soybean oil. All samples were crystallized using fast (7.78°C/min) and slow (0.1°C/min) cooling rates as well as with and without high-intensity ultrasound (HIU, 20 kHz). The 100%, 50%, and 20% samples were crystallized at 38.5, 27.0, and 22.0°C, respectively. HIU was applied at the onset of crystallization and all samples were allowed to crystallize isothermally for 90 min. After 90 min, physical properties such as crystal microstructure, hardness, solid fat content (SFC), elasticity, and melting behavior were evaluated. Physical properties were also measured after storage for 48 h at 22 and 5°C. Results show that OBC was positively correlated with hardness, G′, and SFC after 48 h (r = 0.738, p = 0.006; r = 0.639, p = 0.025; r = 0.695, p = 0.012; respectively), OL was negatively correlated with hardness after 48 h (r = −0.696, p < 0.001), G′ after 90 min and 48 h (r = −0.704, p < 0.001; r = −0.590, p = 0.002), and SFC after 90 min and 48 h (r = −0.722, p < 0.001; r = −0.788, p < 0.001). Neither OBC nor OL were correlated with crystal diameter or the number of crystals.     

Melting and solidification characteristics of confectionery fats: Anhydrous milk fat,cocoa butter and palm kernel stearin blends

Differential scanning calorimetry measurements of crystallization and melting characteristics of commercial samples of anhydrous milk fat (AMF), cocoa butter (CB) and hydrogenated palm kernel stearin (PKS) in ternary blends were studied. Results showed that stabilization at 26°C (either for 40 h or 7 d) did not greatly affect the melting thermogram trace of PKS. However, the effect of stabilization became prominent as CB was added into the system. Deviation of measured enthalpy from the corresponding values, calculated for thermodynamically ideal blends, showed clear interaction between all three fats. At 20°C, the strongest deviation occurred at about the AMF/CB/PKS (1∶1∶1) blend, whereas at 30°C the deviation moved toward the CB/MF (1∶1) blend. The presence of 25% AMF in PKS had little effect on its solidification capability, but solidification was adversely affected with inclusion of CB.     

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.     

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.     

Nonisothermal crystallization behavior of poly(aryl ether ether ketone)

A study has been made of the crystallization behavior of poly(aryl ether ether ketone), PEEK, under nonisothermal conditions. A differential scanning calorimeter (DSC) was used to monitor the energetics of the crystallization process from the melt. For nonisothermal studies, the melt was crystallized by cooling at rates from 1°C/min to 10°C/min. A kinetic analysis based on the recently proposed model for nonisothermal crystallization kinetics to remedy the drawback of the Ozawa equation was applied. The Avrami exponent for the nonisothermal crystallization process was strikingly different from that of the isothermal process, which indicates different crystallization behaviors. The results agree with the morphological observation reported in the literature. This study shows that correct interpretation of the Avrami exponent provides valuable information about the crystal structure and its morphology.     

Effect of cooling rate on crystallization behavior of milk fat fraction/sunflower oil blends

The effect of cooling rate (slow: 0.1°C/min; fast: 5.5°C/min) on the crystallization kinetics of blends of a highmelting milk fat fraction and sunflower oil (SFO) was investigated by pulsed NMR and DSC. For slow cooling rate, the majority of crystallization had already occurred by the time the set crystallization temperature had been reached. For fast cooling rate, crystallization started after the samples reached the selected crystallization temperature, and the solid fat content curves were hyperbolic. DSC scans showed that at slow cooling rates, molecular organization took place as the sample was being cooled to crystallization temperature and there was fractionation of solid solutions. For fast cooling rates, more compound crystal formation occurred and no fractionation was observed in many cases. The Avrami kinetic model was used to obtain the parameters k _n and n for the samples that were rapidly cooled. The parameter k _n decreased as supercooling decreased (higher crystallization temperature) and decreased with increasing SFO content. The Avrami exponent n was less than 1 for high supercoolings and close to 2 for low supercoolings, but was not affected by SFO content.     

Dry Fractionation of Cupuassu (Theobroma grandiflorum) Fat: Physical–Chemical Properties and Polymorphic Behavior

Physical chemical properties of cupuassu fat were modified by dry fractionation. Stearin and olein fractions were obtained at 29, 26, and 24 °C. Polymorphic behavior of unfractionated cupuassu fat (UCF) and its fractions were studied in situ by small-angle (SAXS) and wide-angle (WAXS) X-ray scattering using synchrotron light. Polymorphic transitions were followed in real time tempering samples with a thermal cycle. For UCF, the main polymorphic form crystallized under selected conditions was the β’₂. α and β’₁-forms appeared in trace amounts. β₂-form was obtained after storage at 25 °C for 3 months. Stearins obtained at 26 (S-26) and 24 °C (S-24) showed a similar polymorphic behavior. However, S-26 with improved physical properties might be more suitable for chocolate production or as a trans-fat alternative than UCF. Stearin fraction obtained at 29 °C (S-29) had a complex polymorphic behavior. The α-form was the first polymorphic form detected followed by β’₂-form. There was a polymorphic transition from α to β’₁-form but no transition between β’-forms. They were independent to each other showing fractionation in two different solid solutions. Increased contents of the triacylglycerols (TAG) SOA and SOB together with lower contents of SOO compared to UCF led to co-crystallization because there was no complete compatibility among all TAG present in S-29. β₁-form crystallized after storage forming crystals with a double-layer arrangement and a characteristic morphology. This form could be useful for accelerating crystallization process in melted liquid systems.     

Crystallization Behavior of High-Oleic High-Stearic Sunflower Oil Stearins Under Dynamic and Static Conditions

Soft (SS) and hard (HS) stearins obtained from high-oleic high-stearic sunflower oil were isothermally crystallized under dynamic (with agitation) and static conditions at 16, 17, 18, 19, and 20 °C and 24, 25, 26, 27, and 28 °C, respectively. Both fractions crystallized under the α-form at early stages of crystallization for all temperatures (T _c) tested. Polymorphic behavior strongly changed with T _c and shear conditions for both fractions. SS fractions were characterized by α, β₂ and/or β₁ polymorphs at lower T _c and β₁ crystals at higher T _c when crystallized under dynamic conditions, while this same fat system was characterized by β₂′ crystals at lower T _c and β₂ at higher T _c under static conditions. HS samples were mainly characterized by α and β₂ crystals at lower T _c and α and β₁ crystals at higher T _c when crystallized under dynamic conditions; while the same fat was characterized by β₁′ crystals when crystallized at lower T _c and α when crystallized at higher T _c under static conditions after 90 min at T _c. These different polymorphic behaviors, in combination with the different processing and tempering temperatures are translated in specific textural behavior of the samples.     

Synthesis and crystallization behavior of nylon 12 14. II: Chain‐folded lamellar crystals and crystalline transformation behavior of nylon 12 14

Chain‐folded lamellar crystals of nylon 12 14 have been grown from a dilute 1,4‐butanediol solution with the “self‐seeding” technique. The morphology and structure of nylon 12 14 lamellar crystals were studied by both transmission electron microscopy (TEM) and wide‐angle X‐ray diffraction (WAXD). Two kinds of electron diffraction patterns were detected when different areas were selected for diffraction, which indicates that the α crystal phase and the β crystal phase coexist for nylon 12 14 under the present crystallization conditions. The WAXD diffractograms of the crystal mats confirm the results obtained from electron diffraction (ED). In addition, the changes of the crystal structure as a function of temperature for melt‐crystallized and dilute solution‐crystallized nylon 12 14 were monitored by variable‐temperature WAXD and variable‐temperature infrared spectroscopy (IR). It was found that the melt‐crystallized sample undergoes a Brill transformation at 80°C–90°C, but no Brill temperature can be observed for the dilute solution‐crystallized nylon 12 14.