Induction Time of Crystallization in Vegetable Oils, Comparative Measurements by Differential Scanning Calorimetry and Diffusive Light Scattering

ABSTRACT: In this work we compared the induction time of crystallization (τ_i. measured by DSC (τ_iDSC) and scanning diffusive light-scattering (SDLS, τ_iSDLS) in a vegetable oil blend. Several crystallization temperatures and cooling rates (1,10, and 30 °C/min) were investigated. Additionally, rheograms obtained during the crystallization of the oil blends were obtained to differentiate the stages of nucleation and crystal growth. The results obtained showed that independent of cooling rate and crystallization temperature, SDLS provided an earlier detection of triacylglycerides'(TAGS) nucleation than DSC. Furthermore, τ_iSDLS was more consistent (that is, lower standard deviation) than τ_iDSC particularly at high crystallization temperatures and cooling rates. The rheograms showed that τ_iDSC involves a measurement of crystal growth, while τ_iSDLS is associated with the early formation of a solid phase in the oil blend (that is, TAGS nucleation). When the Fisher-Turnbull equation was therefore used to calculate the free energy of nucleation (ΔG_c), τ_iSDLS provided a better estimate of ΔG_c than that obtained by τ_iDSC     

Influence of a commercial monoacylglycerol on the crystallization mechanism of palm oil as compared to its pure constituents

The effect of a commercial monoacylglycerol (MAG), Myverol™ 18 04-PK (Myverol), on the non-isothermal crystallization mechanism of palm oil (PO) was investigated and compared to the effect of the two main constituents of Myverol, monopalmitin and monostearin. The MAGs were added to PO in concentrations up to 8% and the blends were studied using different techniques (differential scanning calorimetry (DSC), X-ray diffraction (XRD) and polarized light microscopy (PLM)). The DSC crystallization profiles revealed an earlier onset of crystallization along with extra crystallization peaks when MAGs were added to PO. Combined with X-ray results, it could be concluded that the crystallization process of the blends is initiated by the MAGs crystallizing in the α form and then transforming to sub-α. The effect on the non-isothermal crystallization of the PO TAGs is confined to an earlier onset of crystallization, probably through a template effect, and an effect on the crystal structure coarseness.     

L-抗坏血酸棕榈酸酯对椰子油结晶行为的影响

以椰子油作为模型，利用结晶动力学方程、X-射线衍射（XRD）分析、热力学分析以及偏振光显微镜（PLM）观察等方法研究了L-抗坏血酸棕榈酸酯（L-AP）对椰子油结晶行为的影响。结果表明：L-AP提高了椰子油的结晶速率，改变了晶体成核和生长机制；L-AP以“晶种”的方式诱导椰子油的结晶，对其结晶过程产生了促进作用； L-AP没有改变椰子油晶体的晶型以及堆积方式，却增加了晶体纳米片层的厚度；随着L-AP添加量的增加，晶体结构更加致密有序。     

Effect of sugar, cocoa particles and lecithin on cocoa butter crystallisation in seeded and non-seeded chocolate model systems

The effect of major chocolate ingredients (sugar, cocoa particles and lecithin), in combination with the two pre-crystallization techniques, seeding and non-seeding, was investigated with respect to the kinetics of cocoa butter crystallisation and the resulting microstructure. Confocal laser scanning microscopy (CLSM) was used to monitor microstructural evolution under dynamic thermal conditions. DSC measurements and image analysis were also applied in order to quantify the impacts of processing and formulation on microstructure. All ingredients and pre-crystallisation techniques considered proved to have a large impact on fat crystallisation kinetics and the resulting microstructure. Seeded samples tended to form multiple nucleation sites, inducing rapid growth of a crystal network. The non-seeded samples showed an altering structure, with some domains developing large spherical crystals while in other domains a more heterogeneous microstructure resulted. Lecithin showed a remarkable impact on crystallisation kinetics in both the seeded and non-seeded samples. For the seeded samples, the effect was most noteworthy in samples containing cocoa butter and sugar, where lecithin significantly reduced the induction time. In the absence of seeds, lecithin itself acted as the nucleation site for fat crystallisation.     

Crystallization kinetics of emulsified triglycerides

Nucleation and crystal growth process of triglycerides in water emulsions composed of trimyristin (c l4:0) admixed with 0, 40, and 80 ml litre^?1 trilaurin (c 12:0) (expressed v per total v emulsion) were followed with NMR (nuclear magnetic resonance) and DSC (differential scanning calorimetry). Mathematical analysis of the time dependence of the phase changes and thermal data distinguished two distinct ‘apparent’ kinetic phases. These phases were tentatively referred to as nucleation and crystal growth. With 40 and 80 ml litre^?1 trilaurin (NMR data at 293 K) nucleation and crystal growth phases of trimyristin were simulated with zero order and second order rate expressions, respectively. Relative to these mixtures, pure trimyristin nucleation was delayed in the initial phase, but crystal growth occurred with fast homogeneous nucleation and slower growth in the second phase. Statistical analyses indicated that homogeneous nucleation similarly occurred when 40 or 80 ml litre^?1 trilaurin was admixed with trimyristin. NMR resolution made it possible to follow the crystallization phenomena in different locations of the crystallization vessel effectively in situ and undisturbed. Statistical analyses in this case revealed a significant trilaurin-location interaction confirming that the rate of nucleation processes was affected both by the concentration of trilaurin and the heat transfer properties of the sample and vessel. The time-location interactions were not significant, confirming the hypothesis that in the absence of tilaurin, zero order nucleation did not occur in the first phase.     

Effect of Sucrose Esters and Sunflower Oil Addition on Crystalline Microstructure of a High-melting Milk Fat Fraction

ABSTRACT: The effects of sunflower oil (SFO) and the sucrose esters (SE) P-1670, P-170, and S-170 on crystalline microstructure of a high-melting milk fat fraction (HMF) was studied by polarized-light microscopy (PLM) and confocal laser scanning microsopy (CLSM). The addition of SFO markedly diminished crystal size and delayed crystallization kinetics, as observed in PLM images. Addition of P-1670 modified crystallization behavior only slightly. Addition of P-170 and S-170, however, markedly diminished crystal size and led to more transparent crystals, with lower amount of solids in each crystal. These results show that the microstructural properties of HMF were modifed by addition of SFO and by addition of SPE with low HLB.     

Thermal,structural and rheological characteristics of dark chocolate with different compositions

The effect of different cocoa composition of dark chocolate samples and their ingredients on their thermal, structural and rheological characteristics was investigated. Thermal behavior was evaluated by means of differential scanning calorimetry (DSC), while the crystal morphology was observed by polarized light optical microscopy. The rheological measurements were carried out using both continuous and oscillatory experiments. The formation of more stable polymorphic structures was time and temperature dependent; and it was not affected by either cocoa composition or particle sizes. The kinetics of crystallization was determined by a step crystallization method and modeled by the Avrami equation, it was accelerated by solid particles concentration, lower particle size and lower crystallization temperatures. Negative spherulites with featherlike microstructures defined the time dependent crystal growth and were consistent with Avrami indexes of 3–4. Under continuous shear, cocoa butter was well described by the Bingham rheological model, while Casson and Carreau equations modeled the flow of cocoa liquor and chocolate samples. However the Carreau model was preferred for presenting better fittings and for predicting apparent viscosities at low and at high shear rates. From both, continuous and oscillatory experiments, it was found that composition of chocolate samples in terms of fat and nonfat cocoa solids, and sugar content, affected their rheological behavior. The solid liquid transition of chocolate samples and cocoa liquor was obtained at a yield stress of around 1 Pa from both continuous and oscillatory shear experiments.     

Effects of Salts on Crystallization Kinetics and Rheological Behavior of Concentrated α,α-Trehalose Solutions

ABSTRACT The effect of addition of CaCl2 2H2O and MgCl2 6H2O on crystallization kinetics and the rheological behavior of a 70% trehalose solution was studied by polarized light microscopy and dynamic oscillatory rheometry. Salts caused a delay on nucleation with induction times for crystallization longer for Mg2+ than for Ca2+. Divalent cations were incorporated into crystals, changing the growth of certain faces preferentially, which resulted in changes in morphology. Addition of CaCl2 2H2O in a high salt/trehalose molar ratio dramatically increased complex modulus (G*), indicating a stronger viscoelastic behavior. A gel-like structure was formed when Ca2+ was added to trehalose solution. The behavior of Mg2+/trehalose solutions cannot be considered viscoelastic in nature but as a fluid-like system.     

Determination of the Crystallization Behavior of Lipids by Temperature Modulated Optical Refractometry

This study was conducted to examine if the new temperature modulated optical refractometry (TMOR) method is applicable to study the phase behavior of alkyl-based components. n-Hexadecane, palmitic acid, and glycerol tripalmitate were used as model components. TMOR was benchmarked against differential scanning calorimetry (DSC) and polarized light microscopy (PLM). For all substances, a good agreement of the DSC data with TMOR was found. For n-hexadecane, a difference of 2.2 °C for the crystallization and 2.6 °C for the melting temperature was found. Considering palmitic acid, the crystallization temperature differed by 3.3 °C while the melting varied by 2.8 °C. The crystallization temperature of tripalmitate identified by TMOR was 2.7 °C higher, and the melting temperature 2.3 °C was lower compared to the DSC. The crystallization temperature for TMOR was always higher, and the melting temperature was always lower if related to DSC. This leads to the conclusion that TMOR is more accurate and direct. In addition, the transition peaks identified by TMOR were narrower compared to the DSC peaks. This is due to slower heating and cooling rates leading to a smaller temperature range of phase transition and less thermal lag. The study showed that TMOR is an appropriate method to determine the phase transition temperatures for the three examined substances. The results were comparable to the DSC data in both melting and crystallization behavior. Since the accuracy of TMOR is better at lower heating and cooling rates, it could be a reasonable extension of the well-known DSC method in the studies of melting and crystallization.     

Crystallization in Lactose Refining—A Review

In the dairy industry, crystallization is an important separation process used in the refining of lactose from whey solutions. In the refining operation, lactose crystals are separated from the whey solution through nucleation, growth, and/or aggregation. The rate of crystallization is determined by the combined effect of crystallizer design, processing parameters, and impurities on the kinetics of the process. This review summarizes studies on lactose crystallization, including the mechanism, theory of crystallization, and the impact of various factors affecting the crystallization kinetics. In addition, an overview of the industrial crystallization operation highlights the problems faced by the lactose manufacturer. The approaches that are beneficial to the lactose manufacturer for process optimization or improvement are summarized in this review. Over the years, much knowledge has been acquired through extensive research. However, the industrial crystallization process is still far from optimized. Therefore, future effort should focus on transferring the new knowledge and technology to the dairy industry.     

Effect of water and monoglyceride concentration on the behaviour of monoglyceride containing fat systems

The effect of water and monoglycerides on the structural behaviour of a selected fat system was investigated to explore their role in structure development of products like margarine and sponge cake. Firstly, the monoglyceride and triglyceride system was selected based on solid fat content (SFC) determination. This system was further investigated by differential scanning calorimetry (DSC) and polarized light microscopy (PLM). Secondly, the role of water concentration in this system was investigated by SFC-determination and hardness measurements at different water concentrations. These investigations demonstrate clearly the important role of water, especially at lower concentrations. Finally, the influence of monoglycerides on droplet size distribution in margarines and on textural properties of sponge cakes was investigated. These investigations reveal a larger droplet size of monoglyceride containing margarines and a more dense and harder texture of sponge cakes containing monoglycerides.     

水-离子液体混合溶液对玉米淀粉溶解的影响

研究新型离子液体(ionic liquid,IL)-1-烯丙基-3-乙烯基咪唑醋酸盐对普通玉米淀粉溶解性能的影响。采用偏光显微镜(polarized light microscopy,PLM)、X-射线衍射仪(X-ray diffraction,XRD)、差示扫描量热仪(differential scanning calorimetry,DSC)、扫描电子显微镜(scanning electron microscope,SEM)等淀粉表征手段,揭示水和离子液体混合溶液对玉米淀粉溶解的影响。结果发现,通过偏光显微镜和扫描电子显微镜可以观察到在水和离子液体的摩尔比为4∶1时玉米淀粉的颗粒的“马耳他”十字消失,颗粒结构明显变形,从X-射线衍射结果可以看出水和离子液体比为4∶1(摩尔比)处理的玉米淀粉X-射线的衍射峰的峰强度明显减弱,且淀粉的典型A型晶体的特征峰消失,表明淀粉晶体结构遭到严重破坏。通过DSC的结果可以看出,静置60 min后,水∶离子液体为4∶1(摩尔比)处理的淀粉DSC峰没有吸热峰或者放热峰出现,说明相对于其他的比例而言,水和离子液体的比例为4∶1(摩尔比)对淀粉的溶解效果最好。     

Characterization and identification of surface crystals on smear-ripened cheese by polarized light microscopy

Surface crystallization and radial demineralization of Ca, P, and Mg occur in smear-ripened cheese. Furthermore, crystals of ikaite, struvite, calcite, and brushite have been identified in cheese smears by powder X-ray diffractometry (PXRD), and ikaite and struvite exist in smears as single crystals. Polarized light microscopy (PLM) is a simple, inexpensive, and well-established method in geology to detect and identify single crystals. However, use of PLM to identify cheese crystals has not been reported previously. The specific objectives of this research were (1) to identify crystals in cheese smears using selected PLM criteria; (2) to compare identification by PLM against PXRD; and (3) to develop and evaluate a novel treatment for smear material to improve crystal analyses by both PLM and PXRD. Duplicate wheels of 4 cheeses produced by different manufacturers were obtained from retail sources. Scrapings of surface smears were prepared and analyzed by PLM and PXRD by previously described methods. Crystals were categorized by PLM based on angle of extinction (AE), birefringence behavior under crossed polarizers and quartz filters, and size and shape (circularity) by image analysis. Crystals observed by PLM fell almost exclusively into 2 readily differentiated groups based on birefringence behavior and estimated angle of extinction. Group 1 (n = 18) were highly birefringent with AE = 88–92°, whereas group 2 (n = 28) had no birefringence with AE = 13–26°. Group 2 crystals were significantly larger and more circular than group 1 crystals. Group 1 and 2 were identified as struvite and ikaite, respectively, based on known birefringence and AE characteristics. Struvite was identified in all 4 cheeses by PLM but in only 3 cheeses by PXRD. Ikaite was identified in 3 cheeses by PLM but in only 2 cheeses by PXRD. These discrepancies occurred because the smear scrapings from 1 cheese contained excessive amorphous matter that caused extreme background noise, potentially obscuring diffractogram peaks that may have been present. To minimize noise, smear scrapings were dispersed in aqueous NaOH (pH 10) before analyses, which resulted in consistent results by PXRD and PLM. The method also rendered high-quality images by PLM. Data suggest that PLM may offer a simple and inexpensive means to identify struvite, ikaite, and possibly other single crystals in cheese smears.     

Influence of shear on fat crystallization

Processing conditions greatly impact fat crystallization kinetics and growth mechanisms. Recently, there has been increased interest in elucidating the role of shear on fat crystallization. This review provides an overview of fat crystallization under static conditions followed by a summary of the current body of work pertaining to the effects of shear on fat crystallization, namely its effects on nucleation and growth, crystal network formation, polymorphic transitions, and microstructure modification at different length scales. The effects of shear are usually tied to critical shear rates but shear generally enhances nucleation and growth, accelerates crystallization and polymorphic transitions, and can cause orientation and structuring of fat crystal networks.     

聚甲基丙烯酸十八烷基酯/长链脂肪醇共混物的热性能

以物理共混法制备了质量比为60∶40的不同碳链长度脂肪醇和聚甲基丙烯酸十八烷基酯共混物(CnOH/PSMA(60/40)),并利用傅里叶变换红外光谱(FT-IR)、差示扫描量热仪(DSC)、X射线衍射(XRD)、热重分析(TG)和偏光显微镜(POM)等方法对CnOH/PSMA(60/40)共混物的结构、热性能、相转变及结晶行为进行研究。结果表明:对于CnOH/PSMA(60/40)共混物,当n为14、16时共混物出现黑十字消光球晶,尺寸大约在250μm左右;当n为18、26时没有观察到球晶形态。CnOH/PSMA(60/40)共混物的热焓和热稳定性随脂肪醇侧链长度的增加而逐渐增加,并呈现出复杂化的趋势。从结晶成核和侧链结晶角度对共混物的结晶形态进行了探讨,同时分析了共混物作为热能储存材料使用的可能性。     

Characterization and Thermal Stability of Polymorphic Forms of Synthesized Tristearin

ABSTRACT: The polymorphic characteristics and thermal stability of α, β', and β forms of synthesized tristearin were studied using X-ray diffractometry (XRD), differential scanning calorimetry (DSC), polarized light microscopy (PLM), and scanning electron microscopy (SEM). Polymorphic forms of α, β', and β were induced from tristearin melts with increasing temperatures and times. Solid-solid and melt-mediated polymorphic transitions of tristearin occurred predominantly during slow heating rates and rapid heating rates in the DSC, respectively. The stability of α and β forms of tristearin were dependent on storage temperatures. As storage temperatures increased, the rate of polymorphic transitions from α to β and β' to β forms of tristearin increased.     

Crystallization and Drying in Thin Sucrose Films During Panning

Sucrose crystallization in thin films (50–55 μm) was studied, using a videomicroscopy technique, at conditions encountered during hard panning processes. No nucleation occurred in unseeded films, while a linear increase in seeded crystals occurred during drying. Crystal growth rate increased with temperature (25–30°C) and with air velocity (2.4–12.5 m/sec), but did not change with varying sucrose concentrations (70–76% w/w) and relative humidities (0–66% at 30°C). FD & C Yellow No. 5 food coloring in the dye form (0.05–0.5 g/100 mL) showed no effects while similar concentrations in the lake form inhibited crystal growth rate.     

Monoacylglycerols in dairy recombined cream: I. The effect on milk fat crystallization

The effect of monoacylglycerols (rich in oleic acid, stearic acid or lauric acid) on milk fat crystallization in recombined cream is examined using differential scanning calorimetry to study crystallization kinetics, nuclear magnetic resonance to measure solid fat content during storage and interfacial tension analyses to analyze interfacial properties. The long-chain saturated monoacylglycerols (stearic acid) form upon cooling a two-dimensional crystal at the interface, called chain crystallization, which induces interfacial heterogeneous nucleation. Also, the crystal growth and α–β′ polymorphic transition were accelerated. On the contrary, long-chain unsaturated monoacylglycerols (oleic acid) didn't affect the crystallization behavior while mid-chain saturated monoacylglycerols (lauric acid) showed intermediate behavior. None of the monoacylglycerols influenced the solid fat content after storage for 5 days at 5 °C. The observed differences in nucleation mechanism and crystallization kinetics may influence the microstructural arrangement of the milk fat inside the fat globules and consequently the partial coalescence rate and hence the whipping properties of recombined cream.     

Insight in ultrasonic shear reflection parameters by studying temperature and limonene influence on cocoa butter crystallization

In this study an inverse model was developed to derive relevant ultrasonic parameters from ultrasonic shear reflectometry measurements. The inverse model includes four variable parameters: t_ind (induction time), K (crystallization rate), v_s2 (shear ultrasonic velocity) and a_s2 (shear ultrasonic attenuation coefficient). Both the temperature effect and the effect of a minor component limonene (in different concentrations) on the isothermal crystallization of cocoa butter were studied with the ultrasonic shear reflectometry technique and associated inverse model. Subsequently, the ultrasonic parameters were compared with results of conventional techniques to monitor fat crystallization (DSC, PLM). The study shows that t_ind and K provide information on the kinetics of the microstructure development. The parameter v_s2 is related with the equilibrium SFC, while a_s2 is both influenced by the SFC and the organization of the crystals in the network, yielding information about the microstructure of the crystallized samples.Industrial relevanceThe microstructure of crystallized fat determines to a large extent the macroscopic properties of fat rich products, such as texture, mouthfeel,… Hence, monitoring the crystallization behavior (including not only the primary crystallization but also the microstructural development) during the production process is of utmost importance in order to obtain high quality end products. The ultrasonic shear reflectometry technique is a fast non-destructive technique which provides quantitative data about the crystallization process based on an inverse model. The simplicity of the technique offers potential for inline control. This may be beneficial to evaluate the crystallization process under different process conditions and to stimulate product innovation as more insight can be obtained in the microstructure development of new products.     

超声处理对马铃薯淀粉结构特性及理化性质的影响

为了研究超声对马铃薯淀粉微观结构及理化性质的影响,以马铃薯淀粉为原料,通过扫描电子显微镜、激 光共聚焦显微镜、X射线衍射、傅里叶变换红外光谱、差示扫描量热法、快速黏度分析、偏光显微镜观察等方法, 研究了超声对马铃薯淀粉微观结构及理化性质的影响,揭示超声对马铃薯淀粉的机械力化学效应。结果表明：由于 马铃薯淀粉颗粒内部“狭长的脐点区”结构比较疏松,超声处理对马铃薯淀粉可产生显著机械力化学效应;随着超 声时间延长,马铃薯淀粉颗粒内部依次经过受力阶段、聚集阶段、团聚阶段;同时由于超声处理引起了马铃薯淀粉 颗粒结构变化,故导致了马铃薯淀粉理化性质显著变化。