Sonocrystallization of Interesterified Fats with 20 and 30% of Stearic Acid at the sn-2 Position and Their Physical Blends

Physical blends (PB) of high oleic sunflower oil and tristearin with 20 and 30% stearic acid and their interesterified (IE) products where 20 and 30% of the fatty acids are stearic acid at the sn-2 position crystallized without and with application of high intensity ultrasound (HIU). IE samples were crystallized at supercooling temperatures (ΔT) of 12, 9, 6, and 3 °C while PB were crystallized at ΔT = 12 °C. HIU induced crystallization in PB samples, but not in the IE ones. Induction in crystallization with HIU was also observed at ΔT = 6 and 3 °C for IE C18:0 20 and 30% and at ΔT = 9 °C only for the 30% samples. Smaller crystals were obtained in all sonicated samples. Melting profiles showed that HIU induced crystallization of low melting triacylglycerols (TAGs) and promoted co-crystallization of low and high melting TAGs. In general, HIU significantly changed the viscosity, G′, and G″ of the IE 20% samples except at ΔT = 12 °C. While G′ and G″ of IE 30% did not increase significantly, the viscosity increased significantly at ΔT = 9, 6, and 3 °C from 1526 ± 880 to 6818 ± 901 Pa.s at ΔT = 3 °C. The improved physical properties of the sonicated IE can make them good contenders for trans-fatty acids replacers.     

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.     

Effects of High Intensity Ultrasound Frequency and High-Speed Agitation on Fat Crystallization

The objective of this research was to examine the effect of ultrasound frequency and high-speed agitation on lipid crystallization. Interesterified soybean oil was crystallized at 44 °C without and with the application of high intensity ultrasound (HIU—20 and 40 kHz) or with high-speed agitation (6000 and 24,000 rpm). Two tip amplitudes (24 and 108 µm) and three pulse durations were evaluated (5, 10, and 15 s) for the acoustic frequencies tested. Sonication at 20 kHz of frequency significantly reduced crystal size, increased (p < 0.05) elasticity (435.9 ± 173.3–80,218 ± 15,384 Pa) and SFC (0.2 ± 0.0–4.5 ± 0.4%). No significant difference was observed in the crystallization behavior of these samples when sonicated at different amplitudes for 5 and 10 s. The crystallization behavior was significantly delayed (p < 0.05) in samples sonicated using 108 µm amplitude for 15 s. Larger crystals were formed in samples sonicated at 40 kHz compared to those obtained with 20 kHz and lower SFC (3.7 ± 0.0%) and elasticity (3943 ± 1459 Pa) values were obtained. High-speed agitation at 24,000 rpm increased SFC (5.5 ± 0.1%) and crystallized area and decreased the elasticity (42,602 ± 11,775 Pa) compared to the samples sonicated at 20 kHz.     

Sonocrystallization of Interesterified Fats with 20 and 30% C16:0 at <Emphasis Type="Italic">sn</Emphasis>-2 Position

The objective of this study was to induce crystallization in enzymatically interesterified fats (IE) with 20 and 30% palmitic acid at the sn-2 position using high intensity ultrasound (HIU). The physical blends (PB) used to prepare these two IE were consisted of tripalmitin and high oleic sunflower oil and contained 13.2 and 27.1% tripalmitin, respectively. Crystallization behavior of IE was compared with PB at supercoolings of 9, 6 and 3 °C. Results show that the melting point, SFC, and crystallization rate of PB were higher than IE and were driven mainly by tripalmitin content. HIU induced crystallization and generated small crystals in the IE samples. At 9 °C supercooling, sonication did not increase the viscosity of IE C16:0 20%, while that of the IE C16:0 30% increased significantly from 192.4 ± 118.9 to 3297.7 ± 1368.6 Pa·s. The elastic modulus (G’) for IE C16:0 30% increased from 12521 ± 2739.8 to 75076.7 ± 18259 Pa upon sonication at 9 °C supercooling, while the G’ of the IE C16:0 20% did not increase. Similar behavior was observed for the other supercoolings tested. This research suggests that HIU can improve the functional properties of IE with low content of C16:0 creating more viscous and elastic materials. These fats with low C16:0 content and improved functional properties could be used as trans-free fat alternatives.     

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.     

Sonocrystallization of a Tristearin‐Free Fat

The objective of this study was to fractionate a purified interesterified fat to eliminate tristearin (SSS) and to evaluate the crystallization behavior of the tristearin‐free fat. The fractionated sample was crystallized with and without the application of high‐intensity ultrasound (HIU) by supercooling the sample at 2 °C. In the absence of SSS, the crystallization process was driven by low‐melting‐point triacylglycerols (TAG) such as OSS and OOS (O, oleic; S, stearic acid). There were no differences observed in the crystallinity in the sample based on the solid fat content (P > 0.05) along with any microstructural differences. In addition, an increase in the enthalpy of melting was observed upon sonication, indicating higher crystallinity (P < 0.05). Stronger intramolecular forces were formed in the sonicated samples as evidenced by increased viscoelastic parameters such as the elastic modulus (G′) and storage modulus (G″) (P < 0.05). G′ values increased from 138.25 ± 41.30 to 939.73 ± 277.45 Pa while the G″ values increased from 39.15 ± 8.98 to 149.77 ± 16.00 Pa (P < 0.05). Change in viscosity was not observed as a consequence of sonication (P > 0.05). This study showed that HIU was effective in changing the crystallization behavior of SSS‐free fats with low‐melting TAG.     

Impact of high-intensity ultrasound on physical properties and degree of oxidation of lipase modified menhaden oil with caprylic acid and/or stearic acid

The purpose of this research was to determine the effect of high-intensity ultrasound (HIU) on physical properties, degree of oxidation, and oxidative stability of structured lipids (SLs). Caprylic acid (C) and stearic acid (S) were incorporated into menhaden oil using Lipozyme® 435 lipase to obtain five samples: (1) LC 20 (menhaden oil with 20% of C), (2) LC 30 (menhaden oil with 30% C), (3) LS 20 (menhaden oil with 20% S), (4) LS 30 (menhaden oil with 30% S), and (5) Blend C (menhaden oil with 16.24% C and 13.04% S). Samples were crystallized for 90 min at the following temperatures: (1) LC 20 at 15.5°C, (2) LC 30 at 17.5°C, (3) LS 20 at 24°C, (4) LS 30 at 30°C, and (5) Blend C at 18.0°C, and HIU was applied at the onset of crystallization. Physical properties, degree of oxidation, and oxidative stability were evaluated in sonicated and nonsonicated samples. All SLs had statistically higher G′ after sonication. Sonicated LS 30, LC 30, and Blend C had a higher melting enthalpy than the nonsonicated ones, while enthalpy values in sonicated LS 20 and LC 20 samples were not statistically different than the nonsonicated ones. No significant difference between sonicated and nonsonicated samples was observed in peroxide values (1.2 ± 0.1 meq/kg, p > 0.05) and in the oxidative stability index (6.3 ± 0.2 h, p > 0.05). These results showed that HIU was effective at changing physical properties without affecting the oxidation of the samples.     

Use of High-Intensity Ultrasound to Change the Physical Properties of Oleogels and Emulsion Gels

The objective of this work was to evaluate the effect of high-intensity ultrasound (HIU) on the physical properties of a soft oleogel (2% of candelilla wax, 2% of monoacylglycerol, and 2% of hardfat) and of water-in-oil (W/O) emulsion gels (EG) with various amounts of water (0%, 5%, and 25%). Physical properties of these systems such as thermoresistance, microstructure, melting profile, hardness, rheology, and oil loss were measured. When HIU was applied to the oleogel for 3 min using a 3.2 mm-diameter tip at an amplitude of vibration of 216 μm, a reduction in crystal size and crystal area (P < 0.05) was observed with an increase in hardness and no change in G′ nor in oil loss compared to the nonsonicated oleogel. Other sonication conditions (lower power levels, shorter durations, and bigger tips) tested in this study reduced the hardness and elasticity of the sample and increased oil loss. When HIU (3.2 mm-diameter tip, 216 μm, 3 min) was used in emulsions, harder and more elastic (P < 0.05) samples were obtained only in the samples with 25% water. This study shows that the texture of oleogels and EG with 25% of water can be improved by using HIU. The impact of these results is that the fat content of an EG can be reduced by 25% by adding water and HIU can be used to recover the structure lost due to water addition.     

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.     

High-Intensity Ultrasound-Induced Crystallization of Mango Kernel Fat

The crystallization behavior of mango kernel fat (MKF) at 25 °C with and without the application of high-intensity ultrasound (HIU) (20 kHz, 125 W) was studied as a function of ultrasound amplitude level (30%, 50%, and 70% of the maximum amplitude of 180 μm). The irradiation period was fixed at 5 s. It was found that HIU induced MKF crystallization. The crystallization induction time decreased with a decrease in crystal size and an increase in the number of crystals as the HIU amplitude increased. The β' → β transformation was also accelerated with HIU application. This work has shown that there is great potential for the use of HIU in the food industry to achieve a shorter and more controllable crystallization process. In particular, HIU could be used as an efficient tool for controlling the polymorphic transition of fats.     

Optimization of Ethanol-Ultrasound-Assisted Destabilization of a Cream Recovered from Enzymatic Extraction of Soybean Oil

A novel method using ethanol and ultrasound to extract oil from cream obtained from enzyme-assisted aqueous extraction of soybean oil was developed. To evaluate the relationships between operating variables and free oil yield and to maximize the free oil yield, response surface methodology was introduced in this work. The developed regression model was fitted with R ² = 0.9591. Optimized variables were: ethanol concentration of 73 %, ethanol addition volume of 0.55 L/kg, ultrasound power of 427 W, ultrasound time of 47 s, and ultrasound temperature of 53 °C. The free oil yield from the cream under the above conditions was 92.6 ± 3.4 %. Scanning electron microscopy (SEM) was used to evaluate the effect of ultrasonic treatment on ethanol-treated cream, and the SEM images clearly showed that the ultrasound treatment affected dispersing and fracturing of the microstructure of ethanol-treated cream.     

Influence of oxygen atmosphere annealing on the thermal stability of Mn1.2Co1.5Ni0.3O4±δ ceramic films fabricated by RF magnetron sputtering

This paper presents the optimal atmosphere annealing conditions for Mn_1.2Co_1.5Ni_0.3O_4±δ ceramic thin films fabricated by the RF magnetron sputtering method. The microstructure and oxygen distribution, together with electrical properties, are combined and applied for determining thermal stability. All of the Mn_1.2Co_1.5Ni_0.3O_4±δ films, which are annealed at various oxygen atmosphere from 1 × 10^?3 to 1 × 10⁵ Pa, exhibit a negative temperature coefficient characteristic and show a poly-crystalline spinel structure. The film which annealed at 10 Pa with the most uniform and most dense surface morphology has the minimum resistivity compared to the others. It is characterized by the highest Mn³⁺ and Mn⁴⁺ pair content, which gives the highest carrier concentration of ceramic films. Combined with the aging test at 125 °C for 500 h, the films annealed at 10 Pa have the minimum resistance drift (ΔR/R₀ = 2.35%), which is mainly affected by the oxygen vacancy concentration. This demonstrates that the film thermistors annealed in a hypoxia state will never be stable. This is because there will be several oxidation reactions leading to a continuous generation of cationic vacancies during high temperature aging. The present results will open a way to design desired stable negative temperature coefficient thermistors by adjusting the annealing oxygen atmosphere of films.     

Bubble and Crystal Formation in Lipid Systems During High-Intensity Insonation

The objective of the present research was to monitor bubble and crystal formation in lipids during high-intensity insonation. High-intensity ultrasound was generated with a 20-kHz probe. Bubble and crystal formations were recorded using a low-intensity ultrasound spectrometer operating at 1 MHz central frequency. Bubble formation was monitored in soybean oil (SBO) during insonation for different time periods (5, 10 and 60 s) and at different temperatures (22, 24, 26, 28, and 30 °C). Ultrasound attenuation due to the presence of bubbles was observed in all conditions tested. Attenuation increased with temperature and at intermediate frequencies (1 MHz). In addition, the presence of bubbles was detected after insonation was stopped, particularly for SBO sonicated for 60 s at 30 °C. Low-intensity ultrasound spectroscopy was used to monitor the crystallization behavior of interesterified SBO. The acoustic velocity increased during crystallization, but significantly decreased during insonation.     

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.     

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.     

Microstructure characteristic and its influence on the strength of SiC ceramic joints diffusion bonded by spark plasma sintering

The interfacial microstructure evolution and shear strength of SiC joints for high temperature applications diffusion bonded by spark plasma sintering with a Ta-5W interlayer in the temperature range of 1500 °C to 1700 °C were investigated. The interfacial microstructure analysis indicated that (Ta,W)C phase formed initially and (Ta,W)-Si intermetallic compounds subsequently at SiC/Ta-5W interface. Bonding temperature had a significant effect on the reaction layer thickness, which increased with increasing the bonding temperature, and holding time also has an influence on reaction layer thickness. Calculation of diffusion kinetics for the SiC/Ta-5W interface showed that the diffusion constant was about two orders of magnitude larger than that obtained by hot-pressing bonding, and the activation energy was almost one-tenth that of hot-pressing bonding. Both the reaction layer thickness and the interfacial defects had a great effect on the robustness of the joint, and the maximum shear strength of 122 ± 15 MPa was obtained for the joint bonded at 1600 °C for 5 min.     

Effects of Pilot Plant-Scale Ultrasound on Palm Oil Separation and Oil Quality

The effects of ultrasonic standing waves on palm oil separation of ex-screw press feed from the mesocarp of the palm oil fruit, oil recovery and oil quality were determined. The ex-screw press feed at 85 °C was pumped simultaneously into two identical vessels. One vessel was the control (non-ultrasound) and the other vessel (ultrasound) was fitted with two 400 kHz transducer plates operating at 13.4 kJ/kg, which were placed in direct contact with the feed. Oiling-off by gravity settling occurred at faster rates after sonication. The total recoverable oil after 30 min gravity settling and upon centrifuging the underflow sludge (remaining colloidal fraction) at 1000×g was higher after sonication. Total recoverable oil was 30.7 ± 2.9 % and 43.5 ± 8.6 % (w/w original feed basis) for the non-sonicated and sonicated samples respectively. Sonication reduced the oil content of the sludge ex-centrifuge, demonstrating that higher recovery of palm oil was obtained with ultrasound application. Sonication did not affect the DOBI (deterioration of bleachability index) value, and vitamin E and free fatty acid contents of the separated oil. High-frequency ultrasound enhances the separation rate of palm oil and increases oil recovery without compromising oil quality.     

Dense Iodoapatite Ceramics Consolidated by Low‐Temperature Spark Plasma Sintering

Pb_9.85(VO₄)₆I_1.7, a potential waste form for long‐lived I‐129 immobilization, experiences phase decomposition and thus iodine loss at an elevated temperature above 400°C, presenting a significant challenge for effective management of radioactive iodine. In this work, we report low‐temperature consolidation of dense iodoapatite pellets with above 95% theoretical density by spark plasma sintering (SPS) at temperatures as low as 350°C for 20 min without iodine loss. Microstructure analysis indicates a nanocrystalline ceramic with an average grain size less than 100 nm. Grain growth dominates the sintered microstructure at higher temperatures and longer durations. The dense nanoceramics have significantly‐improved fracture toughness as compared with bulk coarsened grain structures. The effects of sintering temperatures (350°C, 400°C, 500°C, and 700°C) and durations (0–20 min) on microstructure, density, fracture morphology, and mechanical properties including Young's modulus and hardness of bulk samples were investigated. Low temperature densified iodoapatites suggest immense potential of SPS as an advanced materials fabrication technology for the development of waste forms for immobilization of volatile radionuclides including radioactive iodine.     

Effect of Storage Conditions and Antioxidants on the Oxidative Stability of Sunflower–Chia Oil Blends

The mixture of different proportions of sunflower with chia oil provides a simple method to prepare edible oils with a wide range of desired fatty acid compositions. Sunflower–chia (90:10 and 80:20 wt/wt) oil blends with the addition of rosemary (ROS), ascorbyl palmitate (AP) and their blends (AP:ROS) were formulated to evaluate the oxidative stability during storage at two temperature levels normally used, cool (4 ± 1 °C) and room temperature (20 ± 2 °C) for a period of 360 days. Peroxide values (PV) of the oil blends with antioxidants stored at 4 ± 1 °C showed levels ≤10.0 mequiv O₂/kg oil; the lowest levels of PV were found for blends with AP:ROS. Values higher than 10.0 mequiv O₂/kg were observed between 120–240 days for oil blends stored at 20 ± 2 °C. Similar trends were observed with p-anisidine and Totox values. The oxidative stability determined by the Rancimat method and differential scanning calorimetry showed a greater susceptibility of the oils to oxidative deterioration with increasing unsaturated fatty acids content. The addition of antioxidants increased the induction time and decreased the Arrhenius rate constant, indicating an improvement in the oxidative stability for all the oil blends. Temperature had a strong influence on the stability of these blends during storage.     

Effects of Particle Size of Sucrose Suspensions and Pre-incubation of Enzymes on Lipase-Catalyzed Synthesis of Sucrose Oleic Acid Esters

The effects of high-speed homogenization, high-intensity ultrasound, and their combination were evaluated for the reduction of the particle size of sucrose crystals to enhance solvent-free lipase-catalyzed synthesis of sucrose oleate at 65 °C. The combination of homogenization and ultrasound greatly decreased the particle size of suspended sucrose crystals in mixtures of oleic acid/sucrose oleate (86 wt% monoester and 14 wt% diester at a ratio of 90/10 w/w) from 88 to 18 μm. The suspension-based medium was charged to a stirred tank bioreactor that also contained immobilized lipase from Rhizomucor miehei or Candida antarctica (Lipozyme^®IM and Novozym^® 435, respectively; Novozymes, Franklinton, NC, USA), that was pre-incubated in oleic acid for several different temperatures (23–60 °C), durations (4–24 h), and stir rates (50–400 rpm, radius of 3 cm), prior to use. The optimal performance was achieved using C. antarctica lipase (83.3 wt% ester, consisting of 46 wt% monoester) in the presence of molecular sieves (18 wt%). The low water concentration (~0.12 wt%) did not affect the activity of C. antarctica lipase.