Induction of Milkfat Crystallization in the Emulsified State by High Hydrostatic Pressure

The effect of high hydrostatic pressure to milk fat in the emulsified state has been studied by transmission election microscopy (TEM) and low resolution pulsed nuclear magnetic resonance (NMR) for the purpose of following pressure-induced crystallization processes. Pasteurized dairy creams (35 and 43% fat) were subjected to pressures between 100 and 500 MPa for 1 to 15 minutes at a temperature of 23°C. By applying the freeze fracture technique for TEM studies it was demonstrated that pressurization induces fat crystallization within the emulsion droplets, predominantly at the globule periphery. The ultrastructural findings were confirmed by NMR which showed that the amount of crystallized fat formed depended both on intensity and time of pressurization. In the pressurized cream samples the crystallization proceeded during further storage at 23°C whereas the fat droplets in the original cream sample remained liquid under these conditions, provided that the cream sample was held at this temperature.     

Interfacial Crystallization of Diacylglycerols Rich in Medium‐ and Long‐Chain Fatty Acids in Water‐in‐Oil Emulsions

The effects of diacylglycerols rich in medium‐ and long‐chain fatty acids (MLCD) on the crystallization of hydrogenated palm oil (HPO) and formation of 10% water‐in‐oil (W/O) emulsion are studied, and compared with the common surfactants monostearoylglycerol (MSG) and polyglycerol polyricinoleate (PGPR). Polarized light microscopy reveals that emulsions made with MLCD form crystals around dispersed water droplets and promotes HPO crystallization at the oil‐water interface. Similar behavior is also observed in MSG‐stabilized emulsions, but is absent from emulsions made with PGPR. The large deformation yield value of the test W/O emulsion is increased four‐fold versus those stabilized via PGPR due to interfacial crystallization of HPO. However, there are no large differences in droplet size, solid fat content (SFC), thermal behavior or polymorphism to account for these substantial changes, implying that the spatial distribution of the HPO crystals within the crystal network is the driving factor responsible for the observed textural differences. MLCD‐covered water droplets act as active fillers and interact with surrounding fat crystals to enhance the rigidity of emulsion. This study provides new insights regarding the use of MLCD in W/O emulsions as template for interfacial crystallization and the possibility of tailoring their large deformation behavior. Practical Applications: MLCD is applied in preparing W/O emulsion. It is found that MLCD forms unique interfacial Pickering crystals around water droplets, which promote the surface‐inactive HPO nucleation at the oil‐water interface. Thus MLCD‐covered water droplets act as active fillers and interact with surrounding fat crystals, which can greatly enhance the rigidity of emulsion. This observation would provide a theoretical reference and practical basis for the application of the MLCD with appreciable nutritional properties in lipid‐rich products such as whipped cream, shortenings margarine, butter and ice cream, so as to substitute hydrogenated oil. MLCD‐stabilized emulsions can also be explored for the development of novel confectionery products, lipsticks, or controlled release matrices.     

Modeling the nucleation and crystallization kinetics of a palm stearin/canola oil blend and lard in bulk and emulsified form

Using high-pressure homogenization to generate different droplet size distributions, the nucleation and crystallization of two fat systems [lard or a plam stearin/canola oil blend (PSCO)] were compared in bulk and emulsified form. Droplet size reduction decreased the final volume fraction of solid fat primarily in the lard system vs. the PSCO system, with a greater reduction in volume fraction using the homogenization regime that led to smaller droplets. Homogeneous and heterogeneous models showed that the nucleation rate generally decreased with a reduction in droplet size. However, the Gibbs surface energy (γ) was significantly underestimated using the homogeneous model, whereas the heterogeneous model fit the data adequately (P<0.05). The temperature sensitivity of the calculated impurity concentration in all emulsified systems was droplet size dependent. The Avrami model showed the emulsified fats to have lower Avrami indices relative to the bulk fat as well as lower crystallization rate constants. Differences in the Avrami indices and the rate constants were more pronounced in the bulk and emulsified PSCO compared with lard.     

Effects of Processing and Composition on the Crystallization and Mechanical Properties of Water-in-Oil Emulsions

This research investigated the role of agitation, high-melting emulsifier and water content on the crystallization process and the texture of water-in-oil emulsions produced on a pilot plant scale using a scraped surface heat exchanger (SSHE). Our results indicated that shear affected the hardness of the emulsions as they exited the SSHE, with softer emulsions processed at higher shear; once the emulsions reached equilibrium temperature, no differences in texture due to shear were observed. The added emulsifier delayed the crystallization of emulsions processed in the SSHE with no further effect on the equilibrium solid fat content (SFC) or textural properties of emulsions after 24 h of storage. The texture of the crystallized emulsions at early stages of processing was influenced by the amount of water and water droplet size; the larger the amount of water and the smaller the droplets, the higher the hardness of emulsions. Once the emulsions reached equilibrium temperature, further crystallization took place, and the texture depended only on the SFC.     

Surface Melting in Alkane Emulsion Droplets as Affected by Surfactant Type

The influence of surfactant type (Tween 20, Tween 40, Tween 60, Tween 80, Brij 58, Triton X-100, SDS, STS) on the crystallization and melting characteristics of emulsified (mean droplet diameter 0.52 μm) n-octadecane and n-eicosane were studied using microcalorimetry. The melting point (~37 °C) of the eicosane droplets was higher than the crystallization point (~24 °C) and was not affected by the surfactant selected. There was a similar separation between the crystallization (~14 °C) and melting (~28 °C) point of the emulsified octadecane however the details of the transitions was affected by the surfactant selected. For Tween 40 and Brij 58-stabilized droplets there was a split peak on crystallization which we attribute to a surface heterogeneous nucleation mechanism. Only these surfactant-alkane combinations had a split peak on melting. The size of the lower temperature fraction decreased with droplet size suggesting another surface effect. However, the size of the surface layer was calculated to be many times the length of the surfactant tail suggesting the crystal structure was modified by the nucleation mechanism.     

Nucleation kinetics of emulsified triglyceride mixtures

The purpose of this study is to determine character istic nucleation parameters such as the surface free energy for nucleus formation in mixtures of fully hydrogenated palm oil (HP) in sunflower oil (SF). These parameters will be used to model the bulk crystallization kinetics of the same mixtures. This was achieved by determining the crystallization kinetics in emulsified triglyceride mixtures using differential scanning calorimetry, proton nuclear magnetic resonance, and ultrasound velocity measurements. The latter technique appeared to be very sensitive for monitoring the crystallization kinetics of fat dispersions containing triglycerides with a simple phase behavior. Isothermal crystallization of emulsified HP stabilized by sodium caseinate started at 7 K below the α clear point, and the kinetics were best fitted assuming heterogeneous nucleation. Isothermal crystallization of emulsified 10% HP in SF stabilized by caseinate started at 14 K below the α melting point, and the kinetics were best fitted assuming homogeneous nucleation. If the same dispersion was stabilized by Tween 20, crystallization started at 11 K below the α melting point, and the kinetics were fitted best using heterogeneous nucleation. Analysis of the temperature dependency of the fit parameters yielded a surface free energy of a nucleus of about 4 mJ.m⁻² in the case of homogeneous nucleation. Pre-exponential nucleation frequencies indicated that a large proportion of the triglyceride molecule should be in the right conformation to be incorporated in a nucleus.     

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.     

Definition of a model fat for crystallization-in-emulsion studies

Numerous food products are dispersed in droplet emulsions in which fat is partially crystallized. A model fat allowing the study of crystallization in emulsion, obtained by the mixing of two fats (one solid and one liquid at room temperature) with simple triacylglycerol (TG) composition, is defined and characterized. Cocoa butter (CB), a vegetable fat mainly composed of monounsaturated long-chain fatty acids (POP, POST, StOSt, where P=palmitic, O=oleic, St=stearic), and miglyol, a synthetic oil made from capric and caprylic fatty acids, were chosen, respectively. The thermal behaviors of CB, miglyol, and their mixtures are studied using high-sensitivity differential scanning calorimetry (DSC). The CB/miglyol ratio was optimized (i) in order to make stable emulsions as a function of time, (ii) so that the mixture displays several solid phases on cooling that result from CB polymorphism, and (iii) in order to keep, even at low temperature, a liquid moiety facilitating the phase transitions. The CB 75%/miglyol 25% composition is defined as the model mixture. This mixture is characterized on cooling at 0.5°C/min by coupled X-ray diffraction as a function of temperature and DSC experiments. First and α 2L (49.3 Å) variety is formed. Then, co-crystallization of both CB and miglyol TG shows the simultaneous formation of longitudinal stackings of 44.5 and 34.5 Å with a lateral organization of β′ form. An unusual TG packing corresponding to compound formation is proposed to explain the observation of a 34.5 Å long-spacing. The crystallization behavior of the model fat mixture dispersed in emulsion droplets is also monitored in order to validate its use.     

Emulsifying properties and surface behavior of native and denatured whey soy proteins in comparison with other proteins. Creaming stability of oil-in-water emulsions

In this work a comparative study of emulsifying and surface behaviors of native whey soy proteins (NWSP) and denatured whey soy proteins (DWSP) with those of native soy isolates, denatured soy isolates (DSI), and sodium caseinate was done. These samples showed different molecular mass distributions in gel filtration profiles. Dissociation and soluble high-M.W. species in DWSP and DSI were observed. Lower interfacial and surface pressure values were obtained with native samples. Thermal treatment and salt addition enhanced tensioactivity in all fractions. Backscattering measurements of all oil-in-water emulsions, which exhibited a trimodal size distribution of droplets, showed the existence of a negative correlation with the median diameter of droplets. Greater droplet sizes were observed with NaCl addition. The NWSP emulsion had the lowest stability against creaming. Denaturation of this sample increased stability and favored air incorporation in emulsions. Destabilization depends not only on median droplet size but also on floc formation and structure. NaCl addition negatively affected the creaming stability only in emulsions formulated with soy isolates. The use of denaturation to enhance the surface and emulsifying properties of whey soy proteins would allow their use in food emulsions.     

Effect of Processing Conditions on the Crystallization Behavior and Destabilization Kinetics of Oil-in-Water Emulsions

The objective of this research was to systematically study the effect of processing conditions on the crystallization behavior and destabilization mechanisms of oil-in-water emulsions. The effect of crystallization temperature (T _c) and homogenization conditions on both thermal behavior and destabilization mechanisms were analyzed. Results show that the crystallization of lipids present in the emulsions was inhibited when compared with bulk lipids as evidenced by a lower onset and peak temperature (T _on and T_p, respectively) in differential scanning calorimetry crystallization exotherms. The smaller the droplet size in the emulsion, the more significant the inhibition (lower T _on and T _p). Lower values of T _on and T _p were not necessarily indicators of emulsion stability. Homogenization conditions not only affected the T _on and T _p of crystallization but also the crystallization profile of the samples. Lipids present in emulsions with small droplets were crystallized and melted in a less fractionated manner when compared to lipids in bigger droplets or even to the bulk lipids. The amount of lipid crystallized as evidenced by enthalpy values, did not have a direct relationship with the emulsions stability. Although enthalpy values increased as T _c decreased, the destabilization kinetics did not follow the same tendency as evidenced by back scattering measurements.     

Effects of vibration blending on the subsequent crystallization behavior of polycarbonate/polypropylene blends

The effects of blending in a novel vibration internal mixer on the subsequent multiple crystallization of 70/30 w/w polycarbonate (PC)/polypropylene (PP) were investigated by differential scanning calorimetry, wide‐angle X‐ray diffractogram, and microscopy. The vibration internal mixer was reformed from a conventional internal mixer through parallel superposition of an oscillatory shear on a steady shear. For this polypropylene‐minor phase blend, three possible crystallization peaks were observed. The crystallization behavior was sensitive to the sizes and the size distribution of the dispersed polypropylene droplets. Larger amplitude and/or higher‐frequency vibration produced more small droplets (<2 μm) and increased the number of medium droplets (2–8 μm) as a result of the spatially wider and temporally quicker variation of shear rate. The resulting subsequent low‐temperature crystallization peak became larger and shifted to lower temperature, and the intermediate‐temperature peak became obvious. On the contrary, the coalescence of small droplets, resulting from the heating treatment, weakened the low‐temperature peak but strengthened the intermediate‐temperature peak and rendered the high‐temperature peak to be wider. Mixing at the too high amplitude produced the unstable, partially cocontinuous phase morphology restricting the medium droplets and enlarging the surface area, such that the intermediate‐temperature crystallization peak did not appear. Multiple crystallization was related to phase morphology and the nucleation density as well as surface effects. Double‐fusion endotherms of the PP component were also observed, corresponding to the melting of different forms of polypropylene crystals. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 92–103, 2002     

Influence of formulation on the thermal behavior of ice cream mix and ice cream

The influence of fat and emulsifier types on particle size and thermal behavior of aged mixes and the corresponding ice creams was investigated. Mixes and ice creams based on partially unsaturated monodiglycerides (MDG) were characterized by an increased percentage of agglomerated fat globules compared with saturated MDG-based system. DSC thermograms obtained for refined coconut oil in mix showed a displacement of the main crystallization event toward lower crystallization teperatures compared with fat in the bulk phase. This supercooling effect was more or less pronounced for the three other fats used (hydrogenated coconut oil, refined palm oil, and anhydrous milk fat). In emulsified systems, an additional exotherm was observed that was interpreted in terms of MDG crystallization. The fact that this peak appeared at different temperatures ranging from 32 to 41°C as a function of the fat selection suggested that different fat-emulsifier interactions would occur. In the case of ice creams, although the water peak interfered with the fat peak, melting DSC curves allowed the discrimination between the fat types used in the formulation     

Aroma Release from Solid Droplet Emulsions: Effect of Lipid Type

Aroma compounds partition between the different phases of a food emulsion and the headspace but only those in the headspace are perceived. Phase transitions in the lipid droplets profoundly affect the position of the partitioning equilibria and hence headspace aroma concentration. The release of four volatile aroma compounds (ethyl butanoate, pentanoate, heptanoate and octanoate) from eicosane, hydrogenated palm fat or Salatrim^® emulsions stabilized with sodium caseinate were investigated as a function of fat crystallization, particle size and droplet concentration. For all compounds, the headspace aroma concentration in equilibrium with solid droplet emulsions was significantly higher than that in equilibrium with liquid droplet emulsions. The partitioning of volatile aroma compounds from emulsion does not depend on the type of liquid lipid, however, the interactions between solid lipid droplets and aroma compounds are significantly influenced by the nature of the crystalline fat. Notably, partitioning into the headspace was much lower for solid triglyceride droplet emulsions than for solid alkane emulsions. It was proposed that both residual liquid lipid in solid triglycerides and aroma co-crystallization with solid lipid could be responsible for higher aroma absorption by solid triglycerides.     

Characterizing cocoa butter seed crystals by the oil-in-water emulsion crystallization method

Unambiguous quantitative evidence for the catalytic action of seed crystals in cocoa butter is presented. We used an ultrasound velocity technique to determine the isothermal growth of solid fat content in cocoa butter oil-in-water emulsions, in which the probability of finding a seed crystal in any one droplet was around 0.37 at 14.2°C. The upper limit for the size of seed crystals in West African cocoa butter was around 0.09 μm, the Gibbs free energy for nucleation was 0.11 mj m⁻², and the concentration of seed crystals was in the range of 10¹⁶ to 10¹⁷ m⁻³. X-ray diffraction measurements showed that emulsified cocoa butter crystallizes in the α polymorph and does not appear to transform to the β′ form within the first 25 min of crystallization. Primary nucleation events in cocoa butter emulsions are accounted for by seed crystals. Collision-mediated nucleation, a secondary nucleation mechanism, in which solid droplets (containing seed crystals) catalyze nucleation in liquid droplets, is shown to account for subsequent crystallization. This secondary nucleation mechanism is enhanced by stirring.     

Encapsulation of oil in silk fibroin biomaterials

Microencapsulation is becoming increasingly important in the food, cosmetics, and medicinal industries due to its potential for stabilization and delivery of volatile and delicate compounds. Novel food‐safe techniques for encapsulating oil in silk biomaterials using emulsion‐based processes that exploit silk's unique properties (including amphiphilicity, biocompatibility, aqueous and ambient processing, and tunable physical crosslinking behavior) are described. The sonication‐induced self‐assembly of silk previously applied to hydrogel fabrication replaced the use of the thermal or chemical suspension crosslinking traditionally used to stabilize the aqueous protein phase in emulsions. Stable, physically crosslinked silk micro‐ and macro‐particles loaded with oil or water‐soluble dye were produced by aliquoting sonicated silk solutions into an oil bath. Oil micro‐droplets emulsified in aqueous silk solutions did not impede the self‐assembly of silk into films or hydrogel networks. In O/W/O emulsions, particle morphology and silk permeability to a model lipophilic dye in the interior phase were controllable via processing. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39990.     

Crystallization dynamics in model emulsions from magnetic resonance imaging

Melt crystallization of trilaurin and trimyristin was investigated in the bulk and in dispersed systems using magnetic resonance imaging. Crystallization rates were studied as a function of time in fat/water (40:60) emulsions containing 0.5% tween 80 and 0.2% xanthan gum to prevent creaming. Oil weighted images were obtained to follow the dynamics of crystallization in the bulk and in an emulsified system. Localized spectroscopy using a stimulated echo pulse sequence was used to quantify the crystallization dynamics pattern at different locations in a trimyristin emulsion (40:60). The results showed that crystallization in the emulsified state occurred over a longer period of time than in the bulk. Imaging allowed for the qualitative visualization of crystallization. Images showed crystallization occurring from the edge to the center. On the other hand, localized spectroscopy allowed for spatially quantitative measurement of the amount of liquid oil, crystalline oil and water. In the trimyristin emulsion (40:60), spectra recorded from the top, center and bottom showed a relatively abrupt crystallization pattern starting earlier at the edges of the container, as previously visualized by the images taken.     

Isothermal crystallization kinetics and melting behavior of multiwalled carbon nanotubes/polyamide‐6 composites

Pristine and functionalized multiwalled carbon nanotubes (MWNTs) were used to fabricate polyamide 6 (PA6) composites through melt blending. The functionalized MWNTs were obtained by grafting 1,6‐hexamethylenediamine (HMD) onto the pristine MWNTs to improve their compatibility with PA6 matrix. The effect of MWNTs on the isothermal crystallization and melting behavior of PA6 was investigated by differential scanning calorimetry (DSC) and X‐ray diffraction (XRD). The Avrami and Lauritzen–Hoffmann equations are used to describe the isothermal crystallization kinetics. The values of the Avrami exponent found for neat PA6, the pristine MWNTs/PA6 and functionalized MWNTs/PA6 composite samples are about 4.0, 1.7, and 2.3, respectively. The activation energies are determined by the Arrhenius method, which is lower for the composites, ?320.52 KJ/mol for pristine MWNTs/PA6 and ?293.83 KJ/mol for functionalized MWNTs/PA6, than that for the neat PA6 (?284.71 KJ/mol). The following melting behavior reveals that all the isothermally crystallized samples exhibit triple melting endotherms at lower crystallization temperature and double melting endotherms at higher crystallization temperature. The multiple melting endotherms are mainly caused by the recrystallization of PA6 during heating. The resulting equilibrium melting temperature is lower for the composites than for neat PA6. In addition, polarizing microscopy (PLM) and small angle light scanning (SALS) were used to study the spherulite morphology. The results show that the MWNTs reduce the spherulite radius of PA6. This reduction is more significant for pristine MWNTs. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Relationship between characteristics of oil droplets and solidification of thermally treated creams

The relationship between the characteristics of oil droplets and the change in appearance of cream was investigated. The model creams (40 wt% oil-in-water emulsion), similar to commerical products, were prepared with vegetable fat, milk protein, and emulsifier. The thermal treatment, in which the cream was exposed to a certain temperature and subsequently recooled, was performed on the assumption that the temperature was temporarily elevated during transportation and storage of commercial products. Solidification of the cream was observed when it was exposed to a temperature where there was a small percentage in solid fat content (SFC) of fat in oil droplets and recooled, whereas the cream remained in the liquid state when it was exposed to the temperature where SFC was zero and recooled. When the SFC of oil droplets was 0% at the treated temperature, greater supercooling prior to fat crystallization occurred and the crystallization rate after the initial formation of crystals was much higher. On the other hand, the polymorphism of fat in the droplets was not directly affected by the thermal treatment. These results indicate that the crystallization in oil droplets at the heating temperature may be closely connected with the destablization of oil droplets via a partial coalescence mechanism, which will cause the solidification of cream.     

Dry fractionation of coconut oil by melt crystallization

Layer melt crystallization was applied for the dry fractionation of multi-component mixtures using coconut oil as a model substance. The aim of the experiments was to optimize the crystallization parameters (e.g. crystallization temperature, melt temperature, cooling rate, agitation speed) in order to obtain the solid fraction with a higher melting temperature and solid fat properties. The isothermal crystallization behavior of coconut oil was investigated via differential scanning calorimetry (DSC). The efficiency of the crystallization process was monitored by determining the melting point and solid fat content (SFC) of the fractionated products. The morphology of crystal layer was studied by a light microscope. Cool finger temperature was found to have the greatest impact on product properties. Applying a cooling rate of 0.2 K/h resulted in sufficient growth rates providing the required products. The micrographs of the solid fraction revealed lamellar particle arrangement compared to coconut oil possessing spherulites.     

Influences of the chemical defects on the crystal thickness and their melting of isothermally crystallized isotactic polypropylene

Ziegler-Natta and Metallocene Catalysis isotactic polypropylene with different chemical defects were isothermally crystallized at various crystallization temperatures. The crystal thickness and their corresponding melting behavior were studied using small angle X-ray scattering, atomic force microscopy, optical microscopy, and differential scanning calorimetry. The equilibrium melt temperature of the samples was calculated from the Hofmann-Weeks extrapolation for the supercooling. Two lamellar populations were distinctly observed in all cases during the crystallization process. Relatively thicker and stable lamellar crystals which melt at higher temperatures were observed with lowering the supercooling and found catalysis dependence in these crystals. During melting, no significant recrystallization of the samples has been detected for higher crystallization temperature where recrystallization processes enhance the lamellae thickness. The melting of the crystals has found strong dependence with the crystallization temperatures, the catalysis process and the nature of the defects present in the isotactic polypropylene. The increase of the crystal lamellae thickness and their melting temperature might be presumably related with the chain folding mechanism as well as the stability of the crystals formed during the isothermal crystallization process. A combined plot of SAXS and DSC results is demonstrated for the equilibrium melting temperature followed by critical analysis of the results.