Crystallization behavior of 1,3‐dipalmitoyl‐2‐oleoyl‐glycerol and 1‐palmitoyl‐2,3‐dioleoyl‐glycerol

A model margarine was stored under a temperature fluctuation cycle of 5—20 °C until granular crystals were observed. Using information obtained from the granular crystals, the crystallization behaviors of major triacylglycerols of palm oil, 1,3‐dipalmitoyl‐2‐oleoyl‐glycerol (POP), 1‐palmitoyl‐2,3‐dioleoyl‐glycerol (POO), and their mixtures were then investigated. It was shown that in the model margarine, the POP content in the granular crystals was higher than in their surrounding materials, and the X‐ray diffraction pattern of the granular crystals revealed that they were the most stable polymorph, β. 99% pure POP, POO, and their mixtures were then stored under the above‐mentioned temperature cycle. POP was found to form the unstable polymorph, α, when cooled rapidly from the melt. Within 24 hours transformation into the γ polymorph and then into the β polymorph was observed. POO was shown to transform into the β' polymorph from α. When POP and POO were mixed, the β polymorph did not emerge, instead it was shown that POP and POO were both agglomerated in the mixtures, giving rise to the formation of granular crystals.     

Effect of Triacylglycerol Compositions and Physical Properties on the Granular Crystal Formation of Fat Blends

The effect of triacylglycerol (TAG) compositions and physical properties related to solid fat content (SFC) on the behavior of granular crystal formation was investigated. Four fat blends involving different 1,3-dipalmitoyl-2-oleoyl-sn-glycerol (POP) and 1-palmitoyl-2,3-dioleoyl-sn-glycerol (POO) compositions or SFC were prepared, and crystallization was investigated using polarizing microscopy, X-ray diffraction, SFC, whereas hardness was determined using a texture analyzer. Samples containing a higher saturated fatty-acid content from palm and higher SFC showed higher β-type crystals in the initial period, yielding a number of small-sized crystals, with no growth occurring afterward. Growth of the granular crystals as a function of time was observed in the samples, transforming from the β’- to β-type polymorph gradually. Large granular crystals at the initial stage were observed in the sample with a higher POO content and lowest SFC. These results suggested that POO promotes the rate of the crystals’ polymorphic transformation, resulting in the growth of granular crystals. In contrast, excess high-melting-point TAG content, such as tripalmitin and POP, retarded granular crystal growth regardless of the increased β’ to β transition rate. We concluded that the behavior of the growth of granular crystals is influenced by the combined effect of TAG composition and SFC.     

Regulating the β′→β polymorphic transition in food fats

Hydrogenated cottonseed oil (HCSO) is commonly used as a β′-stable fat in margarines and shortenings. In the present study, the crystallization behavior of HCSO is altered via dilution, agitation, tempering regime, and the addition of an emulsifier [polyglycerol polyricinoleate (PgPr)]. Key properties assessed include crystal morphology (with polarized light microscopy), polymorphic behavior (with X-ray diffraction), and crystallization kinetics (with DSC). It is demonstrated that on considerable dilution with canola oil (4% w/w), HCSO can be crystallized in the β′ or β polymorph with associated changes in crystal morphology, depending on tempering regime. Crystallization from the melt to 25°C results in the β′-form, as there is insufficient supercooling to form the β polymorph but enough to form the metastable β′. With cooling from the melt to 5°C, there is adequate supercooling for the δ polymorph to form, with the presence of the canola oil facilitating the transformation toward this stable phase. Static vs. crystallization under agitation does not lead to visible changes in either polymorphic behavior or crystal morphology. However, there is extensive secondary nucleation and growth as a result of crystals breaking off accreting agglomerates. The presence of PgPr, added as a crystal modifier, does not affect the final crystal polymorph or morphology, except under one set of conditions—crystallization from the melt to 5°C with agitation, whereby it considerably alters crystallization behavior.     

Thermal and structural properties of sn-1,3-dipalmitoyl-2-oleoylglycerol and sn-1,3-dioleoyl-2-palmitoylglycerol binary mixtures examined with synchrotron radiation X-ray diffraction

Thermodynamic and polymorphic behavior of POP (sn-1,3-dipalmitoyl-2-oleoylglycerol) and OPO (sn-1,3-dioleoyl-2-palmitoylglycerol) binary mixtures was examined using differential scanning calorimetry and conventional and synchrotron radiation X-ray diffraction. A molecular compound, β_C, was formed at the 1:1 (w/w) concentration ratio of POP and OPO, giving rise to two monotectic phases of POP/compound and compound/OPO in juxtaposition. β_C has a long-spacing value of 4.2 nm with a double chainlength structure and the melting point of 31.9°C. A structural model of the POP-OPO compound is proposed, involving the separation of palmitoyl and oleoyl chain leaflets in the double chainlength structure. In the polymorphic occurrence of the POP-OPO mixtures, the POP fraction transformed from α to β′ with no passage through γ, then transformed to β. The presence of OPO in POP promoted the β′-β transformation of POP during the melt-mediated crystallization.     

Crystallization kinetics of palm stearin in blends with sesame seed oil

This study investigates the crystallization kinetics of palm stearin (PS), a palm oil fraction, in blends with sesame seed oil. The results indicate that the crystallization behavior of PS in sesame oil is mainly associated with the crystallization of tripalmitin. Therefore, crystallization of blends of 26, 42, 60, and 80% (wt/vol) PS in sesame oil was described by equations developed for simpler systems (e.g., Fisher and Turnbull equation). The isothermal crystallization, melting profile, and fitting of the kinetics of nucleation to the Fisher and Turnbull equation showed that the 26, 42, and 60% PS/sesame oil blends crystallized mainly in the β₁′ polymorph state. In contrast, the 80% blend crystallized in two different polymorph states (i.e., β₁′ at T⪯307.6 K and β₁ at T≽308.2 K). The data indicated that, in spite of the higher concentration of PS in the 80% PS/sesame oil system, crystallization in the β₁ state required more free energy for nucleation (δG _c ) than β₁′ crystallization in the 26, 42, and 60% PS/sesame oil. At the low cooling rate used (1 K/min) it was observed that, for a particular PS blend, the higher the effective supercooling the higher the viscosity of the oil phase and the smaller the induction time of crystallization (T_i). Additionally, the β₁′ crystals from PS, developed at the highest effective supercooling investigated, were smaller than the β₁ crystals obtained at lower effective supercooling.     

The dsc thermal analysis of crystallization behavior in palm oil,II

Polymorphic behavior of palm oil crystals was investigated by means of a differential scanning calorimeter under isothermal and constant cooling conditions. Constant cooling conditions produced β₁’ crystals mixed with α, and β₂’ crystals. All underwent the typical transformations to the more stable forms; i.e., β₂’ → α → β₁’ → β. Isothermal conditions produced: (a) α crystals mixed with β₁’, (b) transformation from them to β₁, and (c)β₂ and β₃ crystals. In palm oil crystals, sorbitan tristearate retarded the transformation of the unstable α and β’ forms to the stable β form. This retardation, however, was greatly influenced by the cooling and heating conditions. Using that property of sorbitan tristearate, the polymorphic behavior of palm oil crystals could be studied in detail.     

Effect of agglomeration of triacylglycerols on the stabilization of a model cream

This study has been carried out on solidification of a model cream using palm oil as a sole fat source. It was found that the addition of 1‐palmitoylglycerol to palm oil promoted the solidification of the model cream while the addition of 1‐oleoylglycerol had no such effect. Solid fat content of palm oil in the cream with 1‐palmitoylglycerol was found to be lower than those of palm oil and palm oil with 1‐oleoylglycerol after cooling from 60 to 5 °C. Crystallization behaviors of bulk palm oil and mixture of 1, 3‐dipalmitoyl‐ 2‐oleoyl‐glycerol (POP) and 1‐palmitoyl‐2, 3‐dioleoyl‐glycerol (POO) were then studied in the presence of monoacylglycerols. Formation of granular crystals was observed for palm oil and POP/POO mixture in the presence of 1‐palmitoylglycerol. HPLC of the granular crystals revealed that agglomeration of higher melting point triacylglycerols (TAGs) around 1‐palmitolyglycerol took place, which promoted the formation of granular crystals. It was suggested that the agglomeration of higher melting point TAGs around 1‐palmitoylglycerol which was preferentially adsorbed at the oil‐water interface of oil droplets in the model cream led to destabilization of oil‐in‐water emulsion and the solidification of the model cream. At the same time, it was suggested that the fatty acid moiety of emulsifiers played an important role in the agglomeration of TAGs and stabilization of o/w emulsions.     

Polymorphism of POP and SOS III. Solvent crystallization of β2 and β1 polymorphs

Single crystals of β₁ and polycrystals of β₂ of POP and SOS were obtained from acetonitrile solution. The crystallization behavior of the two polymorphs was almost the same in POP and SOS; rapid cooling of the solution preferentially crystallized the metastable β₂ form, and the most stable β₁ form crystallized in a very low solute concentration at the expense of β₂, via solution-mediated transformation. The single crystal of β₂ revealed needle-like irregular shape, whereas well-defined slender rhombic shape was observed in β₁. The solubilities of the β₁ forms of POP and SOS in tetradecane solution were precisely measured in a temperature range of 10∼20°C. This study showed that the solvent crystallization was the single way to grow the β₁ crystal, since melt-cooling and melt-mediated transformation did not crystallize β₁ both in POP and SOS. Presented at 1988 AOCS Annual Meeting at Phoenix.     

Crystallization kinetics of fully hydrogenated palm oil in sunflower oil mixtures

The crystallization kinetics of mixtures of fully hydrogenated palm oil (HP) in sunflower oil (SF) was studied. The thermal properties and phase behavior of this model system were characterized by means of differential scanning calorimetry and X-ray diffraction. From the melting enthalpy and clear point of HP, it was possible to calculate the supersaturation at a given temperature for every composition of the model system. Supersaturation of the model system for the β′ but not for the α polymorph yielded the β′ polymorph, while supersaturation for the α polymorph yielded a mixture of mainly β and some β′ polymorphs. The crystallization kinetics of HP/SF mixtures were determined by pulsed wide-line proton nuclear magnetic resonance for various initial supersaturations in the β′ polymorph. The determined curves were modeled by a modified classical nucleation model and an empirical crystal growth function, which are both functions of supersaturation. Heterogeneous nucleation rates in the β′ polymorph yielded a surface Gibbs energy for heterogeneous nucleus formation of 3.8 mJ·m⁻². About 80% of the triglyceride was assumed to be in a suitable conformation for incorporation in a nucleus. Induction times for isothermal crystallization in the β′ polymorph yielded a surface free energy for heterogeneous nucleus formation of 3.4 to 3.9 mJ·⁻².     

Polymorphism of POP and SOS. II. kinetics of melt crystallization

Melt crystallization of the polymorphs of SOS, α,γ, pseudo-β′, β₂ and β₁. and of POP, α,γ, pseudo-β′₂ pseudo-β ₁, β₂andβ ₁was examined using pure samples (99.9%). Induction time τ for newly occurring crystals in the melt phase was measured with a polarizing microscope equipped with a temperature-controlled growth cell. Rate of crystallization, 1/τ, was obtained for each polymorph of POP and SOS whose identification was done with X-ray diffraction and differential scanning calorimetry (DSC). Two modes of crystallization, melt-cooling and melt-mediation, yielded approximately the same results for POP and SOS: (a) The rates of crystallization were always higher in less stable than in more stable forms,β ₂only crystallized via a γ-melt mediation, butβ ₁did not occur by the melt crystallization; (b) the rate of meltmediated crystallization was always higher than the simple melt-cooling as examined at the same crystallization temperature; (c) the occurrence behavior of the polymorphs differed between the simple-cooling and meltmediation. The results were related to the solidification behavior of the polymorphs of cocoa butter. Presented at the AOCS Annual Meeting in Phoenix, Arizona in May 1988.     

Formation of Granular Crystals in Margarine with Excess Amount of Palm Oil

Crystallization behavior of palm oil and tripalmitin (PPP) in a model margarine system was investigated. The model margarine was held in a programmable oven, heated to 5 °C for 12 h and then 20 °C for a further 12 h. After 3 weeks, the model margarine was evaluated by polarization microscopy. Granular crystals were observed in the margarine containing an excess amount of palm oil and PPP. The concentration of higher-melting fatty acids was higher in the crystals relative to the surroundings. Likewise, the presence of lower-melting fatty acids was lower in the crystals. The polymorphic structure of the margarine with excess palm oil and PPP was determined to be all β′ by X-RD spectra. The result suggested that the agglomeration of higher-melting point triglycerides (TAGs), such as PPP in this study, led to the formation of granular crystals in the margarine without β polymorphic emergence.     

Polymorphism of POP and SOS. I. occurrence and polymorphic transformation

The polymorphic modifications of POP and SOS were identified with X-ray diffraction (XRD), DSC and Raman spectroscopy by using pure samples (99.9%). In POP, six polymorphs, α,γ, pseudo-β′₂, pseudo-β′₁, β′₂ and β′₁, were obtained, whereas five polymorphs, α, γ, pseudo-β′, β₂ and β₁, were isolated in SOS. Thermodynamic stability increased from α to β₁ straightforwardly both in POP and SOS, because the polymorphic transformation went monotropically in the order described above. Additionally, the 99.2% sample of POP crystallized another form, δ, but the 99.9% sample did not, implying subtle influences of the impurity. The four forms, α, γ, β₂ and β₁, of POP, revealed XRD and DSC patterns identical to the four forms of SOS designated by the same symbols. The chain length structure was double inα and triple in the other three forms in both POP and SOS. Peculiarity of POP was revealed partly in the chain length structure of pseudo-β′₂ and pseudo-β′₁ which were double, whereas pseudo-β′ of SOS was triple. This apparently showed contrast to the facts that the three forms revealed rather similar XRD short spacing patterns. Another peculiarity of POP was revealed in enthalpy value of the melt crystallization of α: ΔH_c (α) = 68.1 kJ/mol which was much larger than that of SOS (47.7 kJ/mol), and also than AOA and BOB. These peculiarities mean that the double chain length structures of POP are more stabilized than the others. Raman bands of CH₂ scissoring mode of SOS indicated parallel packing in γ, β₂ and β₁, and orthorhombic perpendicular packing in pseudo-β′. The polymorphic transformation mechanisms were discussed based on the proposed polymorphic structure models. Presented at the AOCS annual meetings in New Orleans, Louisiana in May 1987 and Phoenix, Arizona in May 1988.     

Isothermal crystallization of tripalmitin in sesame oil

Crystallization of tripalmitin (TP) in sesame oil was investigated under isothermal conditions at a cooling rate similar to the one achieved in industrial crystallizers (1 K/min). The results obtained indicated that, at TP concentrations <0.98%, triacylglycerides of sesame oil developed mixed crystals with TP. However, at concentrations within the interval of 0.98 to 3.44%, tripalmitin crystallized independently from sesame oil. Within this concentration interval, discontinuities were observed in the behavior of the induction time of TP crystallization (T _i) in sesame oil as evidenced by differential scanning calorimetry, polarized microscopy studies, and determination of the Avrami index (n). In general, the discontinuities in T _i were associated with different polymorph states developed by TP in sesame oil as a function of its concentration and crystallization temperature. Thus, TP crystals obtained at temperatures above 296 K with 1.80 and 2.62% TP solutions had n values close to 3 and developed lamellar-shaped crystals that are characteristic of β tripalmitin. In contrast, the crystals obtained at temperatures of 296 K and below with 1.80% and 2.62% TP solutions provided n values close to 3. Axialite-shaped β′ TP crystals were obtained under these conditions. For the 0.98% TP solution, simultaneous production of α and β′ crystals occurred below 291 K. However, at temperatures above 291 K, a crystallization process with n=3 was obtained, and it developed a different polymorph state, i.e., β, with lamellar-shaped TP crystals.     

Polymorphism of pos. I. occurrence and polymorphic transformation

Polymorphic behavior of 1,3-rac-palmitoyl-stearoy 1-2-oleoylglycerol, 99.9% purity (POS) was examined by X-ray diffraction (XRD), differential scanning calorimetry (DSC), solubility measurements and optical microscopy in comparison with 1,3-dipalmitoyl-2-oleoylglycerol (POP) and 1,3-distearoyl-2-oleoylglycerol (SOS). Melt crystallization and solvent crystallization were examined for the occurrence of metastable and stable polymorphs. The number of independent polymorphs was four; α,δ, pseudoβ′ andβ. The lowest melting form, α, was identical to that commonly observed in POP and SOS lowest melting forms. As to the highest melting form,β, the XRD shortspacing pattern was identical toβ ₁ of POP and SOS. This is consistent with crystal habit:β single crystals of POS showed the same shape as those of β₁ of POP and SOS. However, the melting point ofβ (POS), 35.9°C, was lower than those ofβ ₁ of POP, 36.7°C, and of SOS, 43.0°C. Correspondingly, solubility ofβ of POS was lower than that of β₁ of POP below about 13°C, but higher above 13°C. POS did not possessβ ₂ , which is the second stable form in POP and SOS. Two forms of6 and pseudoβ′ occurred, the latter being more stable. The structural properties ofδ showed thatδ is not identical toγ previously observed in POP and SOS. Transformation behavior from the metastable to stable polymorphs of POS showed some differences from those of POP and SOS. Presented at the AOCS annual meeting in Cincinnati, Ohio, in May 1989.     

Binary Phase Behavior of 1,3-Dipalmitoyl-2-oleoyl-<Emphasis Type="Italic">sn</Emphasis>-glycerol and 1,2-Dioleoyl-3-palmitoyl-<Emphasis Type="Italic">rac</Emphasis>-glycerol

1,3-Dipalmitoyl-2-oleoyl-sn-glycerol (POP) and 1,2-dioleoyl-3-palmitoyl-rac-glycerol (OOP) are two major molecular species that account for roughly half of the total triacylglycerols in palm oil. The binary phase behavior of a POP/OOP mixture plays an important role in the crystallization of palm oil. We conducted thermodynamic and kinetic studies of OOP and its mixtures with POP using differential scanning calorimetry and X-ray diffraction with a conventional generator and synchrotron radiation. We found that OOP has two polymorphs, α as a metastable form and β′ as the most stable form, and that the two forms are stacked in a triple-chain-length structure. The POP/OOP mixtures exhibited immiscible eutectic natures in both their metastable and their most stable states, in contrast to POP/1,2-dipalmitoyl-3-oleoyl-rac-glycerol and POP/1,3-dioleoyl-2-palmitoyl-sn-glycerol mixtures, in which molecular compounds of a double-chain-length structure were formed. A time-resolved synchrotron radiation X-ray diffraction study undertaken during the cooling and heating processes indicated that the α and β′ forms of the POP and OOP fractions crystallized and melted in separate manners, and that crystallization of the β′ form and the polymorphic transformation from α to β′ of POP and OOP are promoted in the presence of another component. The absence of molecular compound crystals in the binary mixtures of POP/OOP is explained by taking into account the molecular interactions of acyl chain packing, glycerol conformation, and methyl end stacking, among which glycerol conformation appeared to be most influential.     

Sintering of fat crystal networks in oil during post-crystallization processes

Several foods contain semi-solid fats that consist of solid crystals dispersed in a liquid oil. In oil-continuous margarine, butter, and chocolate, fat crystals determine properties such as consistency, stability against oiling-out, and emulsion stability. Trends toward foods with less fat and/or less saturated fat create a need for understanding and controlling the properties of fat crystal dispersions. Fat crystals form a network in oil due to mutual adhesion. One source of strong adhesion is formation of solid bridges (sintering), which has been studied in this work through sedimentation and rheological experiments. Results indicate that sintering may be created by crystallization of a fat phase with a melting point between that of the oil and the crystal. Generally speaking, β′ crystals were sintered by β′ fat bridges, favored by rapid cooling, and β crystals by β fat bridges, favored by slow cooling. The existence of the same polymorphic form of the crystal and bridge indicated that solid bridges, rather than bridges formed by small crystal nuclei, were formed. A maximum in sintering ability for an optimal sintering fat concentration occurred due to competition between bridge formation and other crystallization processes. Some emulsifiers influenced the sintering process. For example, monooolein made it more pronounced, while technical lecithin had the opposite effect.     

Chemical composition and physical properties of soft (tub) margarines sold in Malaysia

Seven samples of domestic and imported Malaysian tub margarines were analyzed for their fatty acid and triglyceride (carbon number) composition, solid fat content, dropping and softening points, crystallization temperature, polymorphic form, color, and textural attributes. Domestic margarines were formulated from palm oil or palm olein and palm kernel oil with a liquid oil but no hydrogenated oils. Two imported products contained hydrogenated palm oil product, which resulted in a high level of β′ crystals, whereas the domestic nonhydrogenated products contained more β than β′ crystals. Crystal habit was related to the fatty acid and triglyceride composition of the high-melting glycerides. Domestic products were firmer in texture, probably because they were formulated to be sold in a tropical climate.     

Tripalmitin-Driven Crystallization of Palm Oil: The Role of Shear and Dispersed Particles

While palm oil (PO) is a reliable ingredient in formulations for biscuits, cream fillings, and compound chocolates, our understanding of its crystallization behavior and physico-chemistry pales in comparison to many other fats and oils. Phase diagrams of triacylglycerol (TAG) mixtures may be used to elucidate fat crystal polymorphism and composition of such oils, yet conditions important to the food industry such as shear speed, relevant processing temperatures, and presence of secondary ingredients are regularly overlooked. Here, the effects of shear speed (n = 0–500 RPM), dispersion concentration (0–5 wt.%), and dispersed particle surface chemistry [silica or octadecyl-functionalized (C18) silica] on the thermal properties of commercial PO when cooled from 60 to 20 °C at 1 °C min⁻¹ were explored, with focus placed on PO's higher-melting fraction. Using a series of high-purity TAG standards, X-ray diffraction revealed PO's higher-melting fraction as mainly composed of tripalmitin (PPP) crystals and molecular compounds (MC) of PPP either with 1,3-dipalmitoyl-2-oleoyl-sn-glycerol (POP) or with POP and 1,2-dipalmitoyl-3-oleoyl-rac-glycerol (PPO) in combination, all in a double chain-length β' (i.e., β'-2) conformation. Shear increased the formation of lower-melting α-2 POP and β'-2 MC_POP:PPO:PPP crystals while depleting the system of β'-2 MC_POP:PPP and β'-2 PPP crystals. This loss was further exacerbated by the addition of dispersed particles to the point where PPP was completely incorporated as MC and β'-2 PPP crystals were eliminated. While heterogeneous nucleation tends to favor kinetic products of fat crystallization, the interactions between shear and surface chemistry varied between crystal types.     

Physical analyses of gel-like behavior of binary mixtures of high- and low-melting fats

Gel-like fat mixtures of high-melting (HM) and low-melting (LM) fats were formed by means of rapid cooling and subsequent heating. No “non-fat” ingredients such as emulsifiers, water, or waxes were added to the mixtures. The gel-like fats having solid fat content (SFC) values below 2.0 wt% formed crystal networks of HM-fats that entrapped the liquid oil fraction of LM-fats. In a search for optimal fat combinations exhibiting gel-like behavior, fully hydrogenated rapeseed oil with a high amount of behenic acid (FHR-B), fully hydrogenated rapeseed oil with a high amount of stearic acid (FHR-S), tristearoylglycerol (SSS), triarachidonoyl-glycerol (AAA), and tribehenoylglycerol (BBB) were examined as the HM-fats. For LM-fats, sal fat olein (SFO), cocoa butter (CB), palm super olein (PSO), and olive oil were examined. The following results were obtained: (i) the gel-like behavior was observed in mixtures of FHR-B/SFO and FHR-B/CB with initial concentrations of FHR-B of 1.5–4.0 wt%. (ii) Rapid cooling to T _c (crystallization temperature) from 70°C and subsequent heating to T _f (final temperature) were necessary to reveal the gel-like behavior, whereas simple cooling without a cooling/heating procedure did not form the gel-like fat mixture. (iii) Optimal values of T _c and T _f were related to the m.p. of the LM-fat and HM-fat, respectively. (iv) Temperature variations of SFC as well as X-ray diffraction spectra showed that the melt-mediated transformation from α to β of the HM-fat crystals was a prerequisite to reveal the gel-like behavior. Consequently, the fat mixture revealing the gel-like behavior might be called β-fat gel.     

The influence of chemical interesterification on the physicochemical properties of complex fat systems. 2. Morphology and polymorphism

Palm oil-soybean oil (POSBO) blends and lard-canola oil (LCO) blends were chemically interesterified with sodium methoxide. Changes in crystal morphology using polarized light microscopy and crystal polymorphic behavior using X-ray diffraction spectroscopy (XRD) were studied. Spherulitic crystalline particles, measuring 10–20 μm, were detected in palm oil (PO). These spherulitic particles were characterized by a dense core surrounded by a lower-density halo region. PO fat-crystal morphology was not greatly altered on addition of soybean oil (SBO), except for a gradual reduction in spherulite size as the amount of SBO in the blends was increased. Chemical interesterification (IE) did not alter PO or POSBO blend fat-crystal morphology significantly. Irregular particles and spherulites of different sizes and shapes were observed in lard, from small crystals to irregular, angular crystal aggregates. Changes in lard fat-crystal morphology due to the addition of canola oil (CO) were concentration-dependent. In general, spherulite diameter decreased with increasing CO addition. IE dramatically altered lard fat-crystal morphology—IE induced the formation of more symmetrical spherulitic crystalline particles, and the halo-to-core ratio was increased significantly. XRD spectroscopic analysis of POSBO blends revealed small changes in the long spacings of PO fat crystals with either blending or IE; all values were close to 45 ?. Short spacings of fat crystals in noninteresterified (NIE) POSBO blends suggested the predominance of β′ polymorphs. IE led to an increase in the proportion of the β polymorph in PO and POSBO blends. Long spacings of NIE lard fat crystals suggested the presence of a bilayer structure in their unit cells (45 ?). Dilution with ≥10% canola oil led to the appearance of a second reflection at 35 ?. β′ polymorphs were predominantly detected in NIE lard and NIE LCO blends. The β polymorph became more evident with increasing addition of CO. Fat crystals in IE lard and IE LCO blends displayed a single long-spacing reflection at 40 ?. IE of lard and LCO blends induced the formation of β polymorphs.