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.     

Thermal analysis of palm mid-fraction,cocoa butter and milk fat blends by differential scanning calorimetry

Commercial samples of anhydrous milk fat (AMF), Ivory Coast cocoa butter (CB) and palm mid-fraction (PMF) were blended in a ternary system. The melting characteristics of the blends were studied by differential scanning calorimetry (DSC). Results suggest that in the studies of interaction involving more than two fats, partial area (A_i) under the melting peak should be converted to partial enthalpy (ΔH_i) rather than to solid fat index. The ΔH values of the blends decreased as the amount of AMF was increased and increased as the amount of CB was increased. In general, the effect of PMF was less pronounced compared to the effect of the other two fats. Eutectic effects within the ternary system could be detected by measuring the deviation of melting enthalpy by DSC, and from the corresponding values that were calculated for the thermodynamically ideal blends. The deviation reached a maximum when the amount of AMF was about 33%. On the binary line of CB/PMF, the eutectic effect was maximum at about 50–75% PMF. The interaction effect in the system was more noticeable at 30 and 20°C than at lower temperatures. Evaluation at 30°C was preferred because both the effect of AMF in the ternary system and the effect of PMF on the binary line were more readily observed.     

Structure evolution and bloom formation in tempered cocoa butter during long‐term storage

Structural evolution in tempered cocoa butter (CB) and CB mixed with a cocoa butter equivalent (CBE) was examined during 26 wk of storage (at 25 °C) using atomic force microscopy, X‐ray powder diffraction, colorimetry and pulsed nuclear magnetic resonance. The form V‐to‐VI polymorphic transition in CB started after 1 week of storage. However, fat bloom was not detected until week 3 when large crystals started to appear on the CB surface. Changes in surface topography coincided with an increase in the surface whiteness index. Addition of CBE delayed bloom development by 1–2 wk. The solid fat content (SFC) of both CB and CB + CBE increased gradually during the early wk of storage before reaching a summit and then decreasing slowly with time (at 25 °C). Concurrently, the surface roughened and the whiteness index increased for both CB and CB + CBE. We postulate that, upon bloom formation, parallel phenomena took place: (i) There was exclusion of triglyceride molecules from the CB and CB + CBE fat crystal networks due to continued contraction, and (ii) less stable crystals melted due to the heat release from the (re)crystallization of liquid fat onto existing surface crystals and from the ongoing form V → VI polymorphic transition. These events resulted in the gradual decrease in SFC seen at longer storage times. In conclusion, this study demonstrated that kinetic and thermodynamic phenomena take place in CB long after it has been tempered.     

Melting behavior of blends of milk fat with hydrogenated coconut and cottonseed oils

The melting behavior of milk fat, hydrogenated coconut and cottonseed oils, and blends of these oils was examined by nuclear magnetic resonance (NMR) and differential scanning calorimetry (DSC). Solid fat profiles showed that the solid fat contents (SFC) of all blends were close to the weighted averages of the oil components at temperatures below 15°C. However, from 15 to 25°C, blends of milk fat with hydrogenated coconut oils exhibited SFC lower than those of the weighted averages of the oil components by up to 10% less solid fat. Also from 25 to 35°C, in blends of milk fat with hydrogenated cottonseed oils, the SFC were lower than the weighted averages of the original fats. DSC measurements gave higher SFC values than those by NMR. DSC analysis showed that the temperatures of crystallization peaks were lower than those of melting peaks for milk fat, hydrogenated coconut oil, and their blends, indicating that there was considerable hysteresis between the melting and cooling curves. The absence of strong eutectic effects in these blends suggested that blends of milk fat with these hydrogenated vegetable oils had compatible polymorphs in their solid phases. This allowed prediction of melting behavior of milk-fat blends with the above oils by simple arithmetic when the SFC of the individual oils and their interaction effects were considered.     

Performance of a Cocoa Butter-Like Fat Enzymatically Produced from Olive Pomace Oil as a Partial Cocoa Butter Replacer

Olive pomace oil is a by-product of olive oil processing and it is considered a low-quality oil. Considering its suitable triacylglycerol (TAG) composition, this work aimed to convert refined olive pomace oil (ROPO) to a cocoa butter (CB)-like fat using sn-1,3 specific lipase, and to investigate its performance as a partial CB replacer. CB-like fat was produced from olive pomace oil by sn-1,3-specific lipase-catalyzed acidolysis in a packed bed reactor. Binary blends of CB and CB-like fat (CB:CB-like fat) were prepared in different proportions, and their physicochemical characteristics [TAG content, melting profile, solid fat content (SFC) and microstructure] were investigated. The contents of 1,3-dipalmitoyl-2-oleoyl-glycerol (POP), 1(3)-palmitoyl-3(1)stearoyl-2-oleoyl-glycerol (POS) and 1,3-distearoyl-2-oleoyl-glycerol (SOS) in the 100:0 blend were 18.9, 33.1 and 24.7%, respectively. These contents decreased to 11.0, 20.0 and 11.7%, respectively, in the 0:100 blend. Although the melting point (28.5 °C) did not change significantly above 30% CB-like fat addition, the shape of the melting peak became wider and irregular. An isothermal solid diagram of SFC showed that better compatibility was observed at temperatures above 35 °C for all blends. Addition of over 30% CB-like fat caused significant difference in the microstructure.     

Chemical and physical characteristics of cocoa butter substitutes, milk fat and malaysian cocoa butter blends

Two ternary systems of confectionery fats were studied. In the first system, lauric cocoa butter substitutes (CBS), anhydrous milk fat (AMF), and Malaysian cocoa butter (MCB) were blended. In the second system, high-melting fraction of milk fat (HMF42) was used to replace AMF and also was blended with CBS and MCB. CBS contained high concentrations of lauric (C_12:0) and myristic (C_14:0) acids, whereas palmitic (C_16:0), stearic (C_18:0), and oleic (C_18:1) acid concentrations were higher in MCB. In addition, AMF and HMF42 contained appreciable amounts of short-chain fatty acids. CBS showed the highest melting enthalpy (143.1 J/g), followed by MCB (138.8 J/g), HMF42 (97.1 J/g), and AMF (72.9 J/g). The partial melting enthalpies at 20 and 30°C demonstrated formation of a eutectic along the binary blends of CBS/MCB, AMF/MCB, and HMF42/MCB. However, no eutectic effect was observed along the binary lines of AMF/CBS and HMF42/CBS. Characteristics of CBS included two strong spacings at 4.20 and 3.8 Å. MCB showed a strong spacing at 4.60 Å and a weak short-spacing at 4.20 Å. On the other hand, AMF exhibited a very weak short-spacing at 4.60 Å and two strong spacings at 4.20 and 3.8 Å, while HMF42 showed an intermediate short-spacing at 4.60 Å and also two strong short-spacings at 4.20 and 3.8 Å. Solid fat content (SFC) analyses at 20°C showed that CBS possessed the highest solid fat (91%), followed by MCB (82.4%), HMF42 (41.4%), and AMF (15.6%). However, at 30°C, MCB showed the highest SFC compared to the other fats. Results showed that a higher SFC in blends that contain HMF does not necessarily correlate with a stronger tendency to form the β polymorph.     

Comparison of lipase-transesterified blend with some commercial solid frying shortenings in Malaysia

A transesterified experimental solid frying shortening was prepared from a palm stearin/palm kernel olein blend at 1∶1 ratio (by weight) by using Rhizomucor miehei lipase at 60°C for 6 h. The fatty acid (FA) and triacylglycerol compositions, polymorphic forms, melting and cooling characteristics, slip melting point (SMP), and solid fat content (SFC) of the transesterified blend were then compared with five commercial solid frying shortenings (three domestic and two imported) found in Malaysia. All the domestic shortenings contained nonhydrogenated palm oil or palm olein and palm stearin as the hard stock, whereas the imported frying shortenings were formulated from soybean oil and cottonseed oil and contained high level of β′ crystals. Trans FA were also found in these samples. The lipase-transesterified blend was found to be more β′-tending than the domestic samples. The SMP of the transesterified blend (47.0°C) fell within the range of the domestic samples (37.8–49.7°C) but was higher than the imported ones (42.3–43.0°C). All samples exhibited similar differential scanning calorimetry cooling profiles, with a narrow peak at the higher temperatures and a broad peak at the lower temperatures, even though their heating thermograms were quite different. Imported samples had flatter SFC curves than both the experimental and domestic samples. The domestic samples were found to have better workability or plasticity at higher temperatures than the imported ones, probably because they were formulated for a tropical climate.     

Physical Properties of Cocoa Butter/Vegetable Oil Blends Crystallized in a Scraped Surface Heat Exchanger

Blends of cocoa butter with soybean oil (CB/SO) or canola oil (CB/CO) were crystallized at either of two agitation rates (100 or 1,000 rpm) and at two process temperatures (14 or 17 °C) in a scraped surface heat exchanger (SSHE). The physical properties were characterized at the SSHE output and during storage (14 and 28 days) at 15 °C. At the SSHE output, the CB/CO and CB/SO systems that had been processed at 100 rpm presented a more solid-like character than systems processed at 1,000 rpm despite the fact that the former systems contained a higher solid fat content than the latter. The degree of secondary crystallization increased with increasing shear rate. Nevertheless, the polymorphic behavior of cocoa butter crystals resembled the behavior observed under static isothermal crystallization conditions. At the SSHE output, systems of either blend contained a mixture of β′ and β crystals. During storage, β′ converted to β in both blends, although it did so to a higher extent in the CB/CO systems. Crystal ripening, observed in the CB/CO blend, provided stability to the systems during storage. In contrast, the CB/SO system increased its hardness by a slow sintering process. The polymorphism and hardness evolution in the blends under study were found to be associated with the molecular compatibility of the triacylglycerols in the cocoa butter and the vegetable oils tested.     

Effect of emulsion temperature on physical properties of palm oil-based margarine

Margarines made from refined, bleached, and deodorized palm oil at different emulsion temperatures showed no significant difference in their consistency, polymorphic behavior, and solid fat content (SFC) during storage, although differences were observed during processing. The emulsion temperatures studied were 40, 45, and 50°C, with other parameters such as emulsion flow rates, tube cooler temperature, and pin rotor speed kept constant. The SFC developed during processing and storage at 28°C was measured to evaluate the quality of margarine. The emulsion contained no SFC at any emulsion temperature studied. However, the amount of SFC in the perfector or tube cooler unit increased to 15.9, 13.9, and 15.6% in margarine produced at emulsion temperatures of 40, 45, and 50°C, respectively. At 40°C, the lowest SFC was developed during storage even though this margarine had the highest consistency. The softening point of this sample was moderately high and closely related to the type of crystal developed, which was a mixture of β′ and β crystals. Emulsion at 45°C gave the most stable margarine consistency and SFC with crystal in the β′ form even after the fourth week. At 50°C, moderately soft product was produced, which might be undesirable for some applications, although the crystals were in the β′ form.     

Attenuation of ultrasonic waves: Influence of microstructure and solid fat content

Ultrasonic technology can be used to monitor the crystallization of fats and determine solid fat content (SFC) online. Ultrasonic waves are attenuated as crystals form and grow, and this attenuation occurs first at higher frequencies. The attenuation of the ultrasonic signal does not depend on the induction times of crystallization of the systems, or on their thermal behavior; but it does depend on SFC and on microstructure, particularly on the crystal size. At low SFC values (≈5%), bigger crystals generate more attenuation. At intermediate SFC values (≈10%), crystal size does not affect signal attenuation and SFC is the key factor responsible for signal attenuation. At high SFC values (up to 20%), crystal size again seems to be the factor that controls attenuation.     

Mixtures of palm kernel oil with cocoa butter and milk fat in compound coatings

Thermal behavior of binary mixtures of palm kernel oil (PKO), cocoa butter (CB), and anhydrous milk fat was used to study mixed-lipid crystallization. This study was related to the physical properties of compound coatings made with these fats. Phase behavior was studied by evaluating changes in melting behavior with composition and time, by creating isosolid diagrams, and by monitoring polymorphic behavior. For binary mixtures, multiple melting peaks and eutectic formation were observed for 30–50% addition levels of CB to PKO, but not for addition of milk fat to PKO. For compound coatings and binary mixtures, made with the same fat composition, hardness of compound coatings increased as solid fat content (SFC) at 25°C of binary mixtures increased. Also, as SFC at 25°C of the binary mixtures increased, induction time for bloom formation and time to fully bloom for compound coatings decreased. Observation of eutectic behavior for binary mixtures indicated softness in a compound coating with the same fat composition, but the converse was not necessarily true.     

Enzymatic Interesterification of Lauric Fat Blends Formulated by Grouping Triacylglycerol Melting Points

Lauric fat blends (appreciable amount of lauric fat with liquid oil and hard fat) initially formulated for shortening production by grouping triacylglycerol (TAG) melting points were further modified by enzymatic interesterification (EIE) to improve their key functionalities as plastic fats. At a similar fat blend formulation, only the high melting fat and medium melting fat were interesterified in binary‐EIE. Meanwhile, both fats and the liquid oil were interesterified in ternary‐EIE. The solid fat content (SFC) of all binary‐EIE blends was generally retained as similar in the temperature range between 0 and 20 °C when the amount of unsaturated TAGs was limited by excluding the liquid oil during EIE. However, the SFC was significantly reduced at temperatures above 20 °C compared to that of the initial blends. Furthermore, the melting point of binary‐EIE blends at BH50H15 formulation prepared with palm stearin and fully hydrogenated rapeseed oil as the hard fat was found to be drastically reduced from 54.6 to 35.3 °C and from 62.8 to 39.2 °C, respectively. In contrast, the SFC of ternary‐EIE blends was generally reduced when more unsaturated TAGs were available for EIE by including the liquid oil. However, higher SFC was noticed at temperatures around 10 °C in ternary‐EIE blends, as the amount of high‐melting fractions in their initial blends was increased from BH50H5 to BH50H15. Eventually, both binary and ternary‐EIE were also found to significantly alter the crystal microstructure of lauric fat blends, in terms of crystal morphology, size and network density.     

Cocoa Butter Alternatives from Enzymatic Interesterification of Palm Kernel Stearin,Coconut Oil,and Fully Hydrogenated Palm Stearin Blends

Structured lipids (SL) were produced from enzymatic interesterification (EIE) of palm kernel stearin (PKS), coconut oil (CNO), and fully hydrogenated palm stearin (FHPS) blends in various mass ratios. The EIE reactions were performed at 60 °C for 6 hours using immobilized Lipozyme RM IM with a mixing speed of 300 rpm. The physicochemical properties, crystallization and melting behavior, solid fat content (SFC), crystal morphology and polymorphism of the physical blends (PB), and the SL were characterized and compared with commercial cocoa butter and cocoa butter alternatives (CBA). EIE significantly modified the triacylglycerol compositions of the fat blends, resulting in changes in the physical properties and the crystallization and melting behavior. SFC and slip melting point of all SL decreased from those of their counterpart PB. In particular, SL obtained from EIE of blends 60:10:30 and 70:10:20 (PKS:CNO:FHPS) exhibited a high potential to be used as trans-free CBA as they showed similar melting ranges, melting peak temperatures, and SFC curves to the commercial CBA with fine needle-like crystals and desirable β' polymorph.     

Effect of TAG composition on the solid fat content profile,microstructure, and hardness of model fat blends with identical saturated fatty acid content

TAGs play an important role in determining the functional properties of fat‐based food products such as margarines, chocolate, and spreads. Nowadays, special attention is given to the role of the TAG structure and how it affects functional properties such as mouth feel, texture, and plasticity. Key to this research is the need to develop more healthy fats with a reduced level of trans and saturated fatty acids (SFAs), while maintaining the desired properties. In this study, fat blends with identical levels of SFA (50%) but differing in the ratio asymmetric/symmetric blends were evaluated by pulsed NMR and texturometry as a function of storage time and storage temperature. A higher trisaturated TAG content gave rise to a higher solid fat content (SFC) at higher temperature and a lower SFC at lower temperature for both palmitic and stearic based blends. On the other hand, the effect of symmetry on the SFC‐profile of the blends was only clear for the stearic based blends. At lower temperatures, the SFC of symmetric TAG based blend (blend SM) was markedly lower than that of asymmetric TAG based blend (blend iS). However, from 30°C onwards, the SFC of blend SM was clearly higher than that of blend iS. The microscopic analyses revealed a denser crystal network for a higher degree of trisaturated TAG and for symmetric stearic based blends. Moreover, some blends showed a clear evolution of the microstructure during storage with smaller crystals transforming into larger ones. Finally, texture analyses demonstrated the importance of the crystallization and storage temperature on the hardness of the blends.     

A Comparison of the Thermo-Physical Behavior of Engkabang (Shorea macrophylla) Seed Fat–Canola Oil Blends and Lard

A study was carried out to compare the thermo-physical behaviors of canola–Engkabang fat blends with those of lard (LD). Four blends were prepared by mixing canola oil with Engkabang fat (CaO/EF) in different ratios: EF-1, 75:25; EF-2, 70:30; EF-3, 65:35; EF-4, 60:40. The fat blends and LD were compared in terms of their basic physicochemical parameters, fatty acid and triacylglycerol (TAG) compositions, melting, solidification, hardness, and polymorphic properties. The slip melting points (SMP) of the fat blends were found to range from 24.8 to 31.2 °C; EF-2 was found to display an SMP value closer to that of LD. With respect to the melting curve of CaO, the melting curves of all fat blends were found to display an additional high-melting thermal transition in the temperature region above 10 °C. The peak maximum of the high-melting thermal transition of EF-3 was the closest to that of LD. The solid fat content (SFC) value of EF-3 was equal to that of LD at 25 °C, whereas the SFC values of EF-2 and LD were similar at 30 to 40 °C. According to textural analysis, EF-2 was found to display a hardness value somewhat closer to that of LD. X-ray diffraction analysis showed that LD and fat blends EF-1, EF-2, and EF-3 display β polymorphic forms.     

Physical properties of interesterified fat blends

Fat blends, formulated by mixing fully hydrogenated soybean oil with nine different commonly used vegetable oils in a ratio of 1:1 (w/w), were subjected to interesterification (also commonly referred to as rearrangement or randomization) with sodium methoxide catalyst. Fatty acid composition and triacylglycerol molecular species of each fat blend and the interesterified product were determined and correlated with the following physical properties: melting, crystallization characteristics and solid fat content. The differences in the endothermic and exothermic peak temperatures, total heat of fusion and crystallization (β and β′ crystalline content) and solid fat content among the fat blends clearly showed the effect of the composition of each oil on the physical properties. Oils that contained a considerable amount of palmitic acid had a favorable influence on the crystallization and polymorphic form of interesterified fat blends.     

Feasibility Study on the Determination of the Solid Fat Content of Fats Using Temperature‐Modulated Optical Refractometry

The solid fat content (SFC) at different temperatures is an important characteristic of fat phases because it correlates to functionality in product applications. Consequently, this characteristic is also used to specify fat compositions in trade. Of three methods applicable, pulsed nuclear magnetic resonance (pMNR) is predominantly applied. Dilatometry and differential scanning calorimetry (DSC) find much less application. Handling with glass vials and high equipment costs make the search for alternatives to pNMR a useful endeavor. Optical refractometry is evaluated with respect to its potential to determine SFC values. Since refractometry is in the first place not suited for suspensions the positive results found are surprising. Applying temperature modulated optical refractometry (TMOR), isothermal optical refractometry with a superimposed temperature undulation yields repeatable results that are highly comparable to pNMR data. For the system studied (palm oil, coconut oil, partially hydrogenated palm oil), TMOR clearly outperforms DSC when pNMR is considered the method of reference. The key finding that refractive index is suitable to determine properties of suspensions is accompanied by the indications that refractometry has the potential to enable competitive methods within the fat technology. Practical Applications: The observation that refractometry can deliver quantitative data on fat suspensions enables the development of an array of new analytical methods. Next to SFC values and melting point, studies on the characterization of polymorphism can be envisioned. Since the device is robust and affordable, it could be in product development and quality control.     

Restructing butterfat through blending and chemical interesterification. 1. Melting behavior and triacylglycerol modifications

Chemical interesterification of butterfat-canola oil blends, ranging from 100% butterfat to 100% canola oil in 10% increments, decreased solid fat content (SFC) of all blends in a nonlinear fashion in the temperature range of 5 to 40°C except for butterfat and the 90∶10 butterfat/canola oil blend, whose SFC increased between 20 and 40°C. The sharp melting associated with butterfat at 15–20°C disappeared upon interesterification. Heats of fusion for butterfat to the 60∶40 butterfat/canola oil blend decreased from 75 to 60 J/g. Blends with >50% canola oil displayed a much sharper drop in enthalpy. Heats of fusion were 30–50% lower on average for interesterified blends than for their noninteresterified counterparts. Both noninteresterified and interesterified blends deviated substantially from ideal solubility, with greater deviation as the proportion of canola oil increased. The change in the entropy of melting was consistently higher for noninteresterified blends than for interesterified blends. Chemical interesterification generated statistically significant differences for all triacylglycerol carbon species (C) from C₃₀ to C_56′ except for C_42′ and in SFC at most temperatures for all blends.     

Dispersed phase destabilization in table spreads

Commercially available butter, regular-fat margarine, and a fat-reduced margarine (38% fat w/w) were stored between 10 and 35°C for up to 4 d to elaborate on the relationship between droplet size and solid fat content (SFC) that exists in these spreads. At 10°C, the mean volume-weighted droplet size for butter was 4.22±0.40 μm followed by margarine (6.22±0.10 μm) and fat-reduced margarine (12.62±0.28 μm). At higher temperatures, as a result of decreasing SFC, the mean droplet size increased as did the droplet size distribution, leading to eventual coalescence and destabilization in all spreads. In butter, the critical SFC was ∼9%, whereas in margarine notable coalescence occurred at ∼5% SFC. The fat-reduced margarine destabilized at lower temperatures than the other spreads (∼20°C vs. ∼30°C), at an SFC of ∼6.5%. In these spreads, two different mechanisms influenced dispersed phase stability: (i) steric stabilization against coalescence via fat crystals located at the droplet interface, known as Pickering stabilization, and (ii) stabilization against droplet sedimentation (and droplet encounters) due to the presence of the fat crystal network.     

Pulsed NMR Method for Solid Fat Content Determination in Tempering Fats Part II: Cocoa Butters and Equivalents in Blends with Milk Fat

Earlier, in part I of this paper, a method for Solid Fat Content (SFC) determination with pulsed NMR has been described for cocoa butters and cocoa butter equivalents. The present work (part II) is a continuation with these fats together with 10 to 30% milk fat. These fat blends need a modified pretreatment before NMR analysis. Crystallisation of the melted fat should be done at 0° C for 150 min and subsequent tempering performed at 19.0° C for 40 h. No other deviations from the earlier reported method have been carried out. Also SFC determination for chocolate has been described and used as a tool for the development of a proper NMR method, giving SFC on a pure fat blend more or less equal to SFC in corresponding milk chocolate. Different pretreatments (i.e. tempering temperatures) have given very different SFC results. A crystallographic understanding of these were achieved using X-ray, microscope and thermal analysis techniques. The chosen tempering temperature 19.0° C gave a single solid solution, which is essential in chocolate if the right properties of the fat are to be reached. Differences in SFC on pure fat blends by different tempering temperatures could, in the same way, be found in milk chocolates stored at corresponding temperatures. Storage temperature can, to a certain degree, be chosen in order to optimize and control the SFC (i.e. properties) in a chocolate product. The choice of initial temperature especially will strongly influence the SFC in chocolate and the crystal lattice remains virtually unaffected by changes in storage temperature.