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.     

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.     

Determination of solid fat content (SFC) of binary fat blends and use of these data to predict SFC of selected ternary fat blends containing low-erucic rapeseed oil

Several oils and fats often used for the industrial preparation of European shortenings were blended in binary systems. The equilibrium (after 48 h at 15°C) solid fat contents (SFC; determined by pulsed NMR spectroscopy) were measured and plotted against blend composition. SFC of the blends resulted from the SFC of each fat for the considered temperature as well as the type of interaction existing between those fats (namely, ideal behavior, monotectic interaction, eutectic interaction, and so on). The type of relationship fitted was dependent on the kind of interaction: Linear relationships were found for total compatibility between fats, and polynomial-type (order 2) relationships were found for fats exhibiting incompatibility. Some corresponding ternary oils and fats blends were also prepared and analyzed. Selected relationships (regression equations of the fitted curves) obtained for binary blends were combined in order to calculate the SFC of the corresponding ternary blends. Experimental values were generally close to predicted ones. The representation of SFC as a function of composition is interesting as it allows one to determine rapidly and easily the type of molecular interaction between two fats and also to determine equations that can be combined to calculate easily the SFC of corresponding ternary blends crystallized in the same way with a good accuracy. The texture (hardness) of several binary and ternary blends was also measured. The combination of the results obtained for SFC with the results obtained for the hardness of binary blends allows the prediction of the hardness of a corresponding ternary blend under the same conditions.     

Comparison of ultrasonic and pulsed NMR techniques for determination of solid fat content

In this work an ultrasonic velocity technique was compared to direct pulsed NMR (pNMR) spectroscopy for the determination of the solid fat content (SFC) of anhydrous milk fat (AMF), cocoa butter (CB), and blends of AMF and CB with canola oil (CO) in the range 100 to 70% (w/w). In situ measurements of ultrasonic velocity were carried out during cooling (50–5°C) and heating (5–50°C) of the fat samples, and SFC values were calculated. The SFC were also determined simultaneously by pNMR. Peak melting temperatures determined by DSC were used as an indicator of the polymorphic state of the different fats and fat blends. Estimates of SFC obtained using pNMR and ultrasonic velocimetry did not agree. Our results suggested that ultrasonic velocity was highly dependent on the polymorphic state of the solid fat. Ultrasonic velocity in fat that contained crystals in a more stable polymorphic form was consistently higher than in fat that contained crystals in a less stable polymorphic modification. A high attenuation of the signal was observed in milkfat and CB at lower temperatures, particularly after sitting for 24 h. This high attenuation could be a product of scattering by crystallites or by microscopic air pockets formed upon solidification of the material, or it could be due to high ultrasonic absorption associated with phase transitions. This research highlights some of the problems associated with applying ultrasonics to the determination of SFC.     

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.     

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.     

The influence of chemical interesterification on physicochemical properties of complex fat systems 1. Melting and crystallization

The effects of blending palm oil (PO) with soybean oil (SBO) and lard with canola oil, and subsequent chemical interesterification (CIE), on their melting and crystallization behavior were investigated. Lard underwent larger CIE-induced changes in triacylglycerol (TAG) composition than palm oil. Within 30 min to 1 h of CIE, changes in TAG profile appeared complete for both lard and PO. PO had a solid fat content (SFC) of ∼68% at 0°C, which diminished by ∼30% between 10 and 20°C. Dilution with SBO gradually lowered the initial SFC. CIE linearized the melting profile of all palm oil-soybean oil (POSBO) blends between 5 and 40°C. Lard SFC followed an entirely different trend. The melting behavior of lard and lard-canola oil (LCO) blends in the 0–40°C range was linear. CIE led to more abrupt melting for all LCO blends. Both systems displayed monotectic behavior. CIE increased the DP of POSBO blends with ≥80% PO in the blend and lowered that of blends with ≤70% PO. All CIE LCO blends had a slightly lower DP vis-à-vis their noninteresterified counterparts.     

The effect of supercooling on crystallization of cocoa butter-vegetable oil blends

The solid fat content (SFC), Avrami index (n), crystallization rate (z), fractal dimension (D), and the pre-exponential term [log(γ)] were determined in blends of cocoa butter (CB) with canola oil or soybean oil crystallized at temperatures (T _Cr) between 9.5 and 13.5°C. The relationship of these parameters with the elasticity (G′) and yield stress (σ^*) values of the crystallized blends was investigated, considering the equilibrium melting temperature (T _M ^o) and the supercooling (i.e., T _Cr ^o−T _M ^o) present in the blends. In general, supercooling was higher in the CB/soybean oil blend [T _M ^o=65.8°C (±3.0°C)] than in the CB/canola oil blend [T _M ^o=33.7°C (±4.9°C)]. Therefore, under similar T _Cr values, higher SFC and z values (P<0.05) were obtained with the CB/soybean oil blend. However, independent of T _Cr TAG followed a spherulitic crystal growth mechanism in both blends. Supercooling calculated with melting temperatures from DSC thermograms explained the SFC and z behavior just within each blend. However, supercooling calculated with T _M ^o explained both the SFC and z behavior within each blend and between the blends. Thus, independent of the blend used, SFC described the behavior of G′_eq and σ^* and pointed out the presence of two supercooling regions. In the lower supercooling region, G′_eq and σ^* decreased as SFC increased between 20 and 23%. In this region, the crystal network structures were formed by a mixture of small β′ crystals and large β crystals. In contrast, in the higher supercooling region (24 to 27% SFC), G′_eq and σ^* had a direct relationship with SFC, and the crystal network structure was formed mainly by small β′ crystals. However, we could not find a particular relationship that described the overall behavior of G′_eq and σ^* as a function of D and independent of the system investigated.     

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.     

Physical properties of lipase‐catalyzed interesterification of palm stearin with canola oil blends

Interesterified blends of hard palm stearin (IV of 11) and canola oil (hPS/CO) in ratios of 20 : 80, 30 : 70, 40 : 60, 50 : 50, 60 : 40 and 70 : 30 were prepared using immobilized Thermomyces lanuginosus lipase (Lipozyme TL IM). Comparison of physical properties was carried out between non‐interesterified and enzymatically interesterified products by monitoring their slip melting point (SMP), solid fat content (SFC), melting thermogram and polymorphism behavior. The Lipozyme TL IM‐catalyzed interesterification significantly modified the physical properties of the hPS:CO blends. The results showed that all the interesterified blends had lower SMP and SFC than their unreacted blends. The SMP result showed that the interesterified blends of hPS/CO 40 : 60, 50 : 50 and 60 : 40 could be useful for stick margarine and shortening applications, respectively. From the SFC analysis, the interesterified blends of hPS/CO 40 : 60 have SFC curves similar to vanaspati. The interesterified blends of hPS/CO 50 : 50 and 60 : 40 have SFC curves similar to margarines, puff pastry margarine and shortening. Interesterification had replaced the higher‐ and lower‐melting triacylglycerols by the middle‐melting triacylglycerols, yielding mixtures of lower SMP and SFC, compared to the original palm stearin. X‐ray diffraction analysis indicated the appearance of β' crystals in all the interesterified hPS/CO blends from predominantly β‐type oils.     

Trans‐free fats through interesterification of canola oil/palm olein or fully hydrogenated soybean oil blends

Binary blends of canola oil (CO) and palm olein (POo) or fully hydrogenated soybean oil (FHSBO) were interesterified using commercial lipase, Lypozyme TL IM, or sodium methoxide. Free fatty acids (FFA) and soap content increased and peroxide value (PV) decreased after enzymatic or chemical interesterification. No difference was observed between the PV of enzymatically and chemically interesterified blends. Enzymatically interesterified fats contained higher FFA and lower soap content than chemically prepared fats. Slip melting point (SMP) and solid‐fat content (SFC) of CO and POo blends increased, whereas those of CO and FHSBO blends decreased after chemical or enzymatic interesterification. Enzymatically interesterified CO and POo blends had lower SMP and SFC (at some temperatures) than chemically interesterified blends. The status was reverse when comparing chemically and enzymatically interesterified CO and FHSBO blends. The induction period for oxidation at 120°C of blends decreased after interesterification. However, chemically interesterified blends were more oxidatively stable than enzymatically interesterified blends. Interesterified blends of CO and POo or FHSBO displayed characteristics suited to application as trans‐free soft tub, stick, roll‐in and baker's margarine, cake shortening and vanaspati fat.     

Physicochemical and Rheological Properties of Crystallized Blends Containing <Emphasis Type="Italic">trans</Emphasis>-free and Partially Hydrogenated Soybean Oil

Three vegetable oil blends, intended for formulation of high melting temperature confectionary coatings, were prepared by mixing different proportions of coconut oil, palm stearin, and either partially hydrogenated soybean oil (PH-SBO) or native soybean oil (i.e., trans-free SBO). The blends were crystallized under the same isothermal conditions and the crystallized systems evaluated by DSC, SFC, polarized light microscopy, and rheology under low [i.e., G′ and yield stress (σ*)] and high (i.e., creep and recovery profiles) stress forces. Overall, all trans-free blends showed lower SFC and heat of crystallization than the ones obtained with PH-SBO blends. These results showed that trans-fatty acids decrease the level of structural order of the crystals, and probably also the organization of the crystal network. As a result, most of the crystallized blends with PH-SBO showed lower σ* values and higher creep profiles (i.e., softer texture) than trans-free blends, particularly in systems crystallized at high supercooling and blends with saturated medium chain TAG. Nevertheless, at particular crystallization temperatures some trans-free formulations provided crystallized systems with rheological properties that would result in softer textures than the ones obtained with PH-SBO blends. Knowledge of the rheological properties under low and high stress forces is vital when comparing the functionality of crystallized TAG systems with and without TAG with trans-fatty acids.     

Effect of Tempering on the Texture and Polymorphic Behaviour of Margarine Fats

Separated fats from commercial soft (soft fat) and stick (stick fat) margarines and mixtures of hydrogenated super olein (H-olein) and canola oil, were temperature cycled between 4°C and 15,20 and 25°C. The polymorphic form, SFC and texture of the fats were evaluated. Temperature cycling of soft fats between 4 and 20°C resulted in the crystals being either in the β polymorphic form or mixtures of β′ and β. When temperature cycled between 4 and 15°C the presence of β′ crystals was improved, but there were soft fats that after the fourth cycle contained only β crystals. When stick fats were temperature cycled between 4 and 20°C, the crystals after the fourth cycle were either in the β′ form or contained mixtures of β′ and β. Mixtures of H-olein-canola showed superior β′ stability throughout. A mixture of 20% H-olein/canola oil compared well with the SFC and texture of soft margarines while a mixture of 40% H-olein/canola oil with those of stick margarines. Texture was evaluated by constant speed penetration. Texture of fats is very dependent on temperature history. DSC-crystallization curves of the fats showed a variety of patterns.     

Changing the SFC Profile of Lauric Fat Blends Based on Melting Group Triacylglycerol Formulation

Lauric fat blends could be prepared from formulation of different melting triacylglycerol (TAG) group to obtain various desired SFC profiles as required by different fat rich products such as margarine and shortening. At the interval temperature from 0 to 20 °C, an increase ratio of body and heated (BH) melting TAG group in the fat blends imposed higher SFC values with steeper SFC slopes. Meanwhile, at the interval temperature from 20 to 40 °C, an increase ratio of heated (H) melting TAG group resulted higher SFC values with comparable SFC slopes. The use of Palm Stearin (PS) or Fully Hydrogenated Rapeseed Oil (FHRO) as the hard fat gave comparable SFC profiles but the fat blends with FHRO melted completely (SFC 0 %) at higher temperature (60 °C) while those of PS did not. In addition, the crystallization and melting behaviors of lauric fat blends as measured by DSC were influenced by different ratio of TAG distribution formulated at H15 (varied BH) and BH50 (varied H). Fat blends with PS also showed different crystal morphology compared to those with FHRO as measured by PLM.     

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.     

<Emphasis Type="Italic">In situ</Emphasis> monitoring of solid fat content by means of pulsed nuclear magnetic resonance spectrometry and ultrasonics

An ultrasonic technique was developed to study the crystallization process of edible fats on-line. A chirp wave was used instead of the conventional pulser signal, thus achieving a higher signal-to-noise ratio. This enabled measurements to be made in concentrated systems [≈20% solid fat content (SFC)] through a 8.11-cm thick sample without significant signal loss. Fat samples were crystallized at 20, 25, and 30°C at a constant agitation rate of 400 rpm for 90 min. The crystallization process was followed by ultrasonic spectroscopy and a low-resolution pulsed nuclear magnetic resonance spectrometer. Specific relationships were found between ultrasonic parameters [integrated response, time of flight (TF), and full width half maximum] and SFC. TF, which is an indirect measurement of the ultrasonic velocity (v), was highly correlated to SFC (r ²>0.9) in a linear fashion (v=2.601 SFC+1433.0).     

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.     

<Emphasis Type="Italic">Trans</Emphasis>-Free Plastic Shortenings Prepared with Palm Stearin and Rice Bran Oil Structured Lipid

Rice bran oil structured lipid (RBOSL) was produced from rice bran oil (RBO) and the medium chain fatty acid (MCFA), caprylic acid, with Lipozyme RM IM as biocatalyst. RBOSL and RBO were mixed with palm stearin (PS) in ratios of 30:70, 40:60, 50:50, 60:40 and 70:30 v/v (RBOSL to PS) to formulate trans-free shortenings. Fatty acid profiles, solid fat content (SFC), melting and crystallization curves and crystal morphology were determined. The content of caprylic acid in shortening blends with RBOSL ranged from 9.92 to 22.14 mol%. Shortening blends containing 30:70 and 60:40 RBOSL or RBO and PS had fatty acid profiles similar to a commercial shortening (CS). SFCs for blends were within the desired range for CS of 10–50% at 10–40 °C. Shortening blends containing higher amounts of RBOSL or RBO had melting and crystallization curves similar to CS. All shortening blends contained primarily β′ crystals. RBOSL blended with PS was comparable to RBO in producing shortenings with fatty acid profiles, SFC, melting and crystallization profiles and crystal morphologies that were similar. RBOSL blended with PS can possibly provide healthier alternative to some oils currently blended with PS and commercial shortening to produce trans-free shortening because of the health benefits of the MCFA in RBOSL.     

Modification of margarine fats by enzymatic interesterification: Evaluation of a solid-fat-content-based exponential model with two groups of oil blends

Lipozyme TL IM-catalyzed interesterification for the modification of margarine fats was carried out in a batch reactor at 70°C with a lipase dosage of 4%. Solid fat content (SFC) was used to monitor the reaction progress. Lipase-catalyzed interesterification, which led to changes in the SFC, was assumed to be a first-order reversible reaction. Accordingly, the change in SFC vs. reaction time was described by an exponential model. The model contained three parameters, each with a particular physical or chemical meaning: (i) the initial SFC (SFC₀), (ii) the change in SFC (ΔSFC) from the initial to the equilibrium state, and (iii) the reaction rate constant value (k). SFC_o and ΔSFC were related to only the types of blends and the blend ratios. The rate constant k was related to lipase activity on a given oil blend. Evaluation of the model was carried out with two groups of oil blends, i.e., palm stearin/coconut oil in weight ratios of 90∶10, 80∶20, and 70∶30, and soybean oil/fully hydrogenated soybean oil in weight ratios of 80∶20, 65∶35, and 50∶50. Correlation coefficients higher than 0.99 between the experimental and predicted values were observed for SFC at temperatures above 30°C. The model is useful for predicting changes in the SFC during lipase-catalyzed interesterification with a selected group of oil blends. It also can be used to control the process when particular SFC values are targeted.     

Phase Behavior of Palm Oil in Blends with Palm-Based Diacylglycerol

Phase behavior of palm oil (PO) in blends with different concentrations (10% intervals) of palm-based diacylglycerol oil (PO-DAG) was studied using the iso-solid diagram, solid fat content (SFC) with the hardness thermal protocol, DSC melting and crystallization curves, X-ray diffraction curves, and texture analysis (hardness). Minor eutectic effects were observed at around 20–50% PO-DAG in 20–50% SFC iso-lines. The phase behavior predicted by the iso-solid diagram as well as SFC with the hardness thermal protocol did not account for hardness variations observed between PO and PO blends with 10–40% PO-DAG. Nevertheless, the latter could be attributed to the corresponding DSC data as well as crystal polymorphism. However, as the concentration of PO-DAG increased from 40% to 100%, iso-line temperatures, SFC with the hardness thermal protocol, and also hardness were found to steadily increase. PO-DAG at 10% concentration was found to have a β′-stabilizing effect on the polymorphism of PO, while a β-tending effect was observed as the concentration of PO-DAG increased from 10% to 90%.