Physicochemical and Oxidative Changes in Sonicated Interesterified Soybean Oil

The effect of power ultrasound on physicochemical properties and oxidative stability of an interesterified soybean oil (IESBO) was investigated. IESBO was crystallized at 32 °C and sonicated for 10 s with acoustic power of 101 W. The sonicated IESBO was tested for melting behavior and chemical composition and compared to those of non sonicated IESBO to determine physical and chemical changes originated as a consequence of sonication. Application of power ultrasound affected the melting behavior of the crystallized fat and did not affect its chemical composition. Oxidation stability of the sonicated IESBO was measured using peroxide value (PV) and compared to that of non sonicated IESBO and liquid soybean oil (SBO) when stored at 25 °C for 105 days followed by storage at 40 °C for 42 days. Power ultrasound did not cause accelerated oxidation in SBO or IESBO until they were highly oxidized (PV > 10 mequiv/kg). At high levels of oxidation, non‐sonicated IESBO had significantly higher PV than sonicated IESBO, while non‐sonicated SBO had significantly lower PV than sonicated SBO.     

Impact of high-intensity ultrasound on physical properties and degree of oxidation of lipase modified menhaden oil with caprylic acid and/or stearic acid

The purpose of this research was to determine the effect of high-intensity ultrasound (HIU) on physical properties, degree of oxidation, and oxidative stability of structured lipids (SLs). Caprylic acid (C) and stearic acid (S) were incorporated into menhaden oil using Lipozyme® 435 lipase to obtain five samples: (1) LC 20 (menhaden oil with 20% of C), (2) LC 30 (menhaden oil with 30% C), (3) LS 20 (menhaden oil with 20% S), (4) LS 30 (menhaden oil with 30% S), and (5) Blend C (menhaden oil with 16.24% C and 13.04% S). Samples were crystallized for 90 min at the following temperatures: (1) LC 20 at 15.5°C, (2) LC 30 at 17.5°C, (3) LS 20 at 24°C, (4) LS 30 at 30°C, and (5) Blend C at 18.0°C, and HIU was applied at the onset of crystallization. Physical properties, degree of oxidation, and oxidative stability were evaluated in sonicated and nonsonicated samples. All SLs had statistically higher G′ after sonication. Sonicated LS 30, LC 30, and Blend C had a higher melting enthalpy than the nonsonicated ones, while enthalpy values in sonicated LS 20 and LC 20 samples were not statistically different than the nonsonicated ones. No significant difference between sonicated and nonsonicated samples was observed in peroxide values (1.2 ± 0.1 meq/kg, p > 0.05) and in the oxidative stability index (6.3 ± 0.2 h, p > 0.05). These results showed that HIU was effective at changing physical properties without affecting the oxidation of the samples.     

Use of High-Intensity Ultrasound to Change the Physical Properties of Oleogels and Emulsion Gels

The objective of this work was to evaluate the effect of high-intensity ultrasound (HIU) on the physical properties of a soft oleogel (2% of candelilla wax, 2% of monoacylglycerol, and 2% of hardfat) and of water-in-oil (W/O) emulsion gels (EG) with various amounts of water (0%, 5%, and 25%). Physical properties of these systems such as thermoresistance, microstructure, melting profile, hardness, rheology, and oil loss were measured. When HIU was applied to the oleogel for 3 min using a 3.2 mm-diameter tip at an amplitude of vibration of 216 μm, a reduction in crystal size and crystal area (P < 0.05) was observed with an increase in hardness and no change in G′ nor in oil loss compared to the nonsonicated oleogel. Other sonication conditions (lower power levels, shorter durations, and bigger tips) tested in this study reduced the hardness and elasticity of the sample and increased oil loss. When HIU (3.2 mm-diameter tip, 216 μm, 3 min) was used in emulsions, harder and more elastic (P < 0.05) samples were obtained only in the samples with 25% water. This study shows that the texture of oleogels and EG with 25% of water can be improved by using HIU. The impact of these results is that the fat content of an EG can be reduced by 25% by adding water and HIU can be used to recover the structure lost due to water addition.     

Sonocrystallization of a Tristearin‐Free Fat

The objective of this study was to fractionate a purified interesterified fat to eliminate tristearin (SSS) and to evaluate the crystallization behavior of the tristearin‐free fat. The fractionated sample was crystallized with and without the application of high‐intensity ultrasound (HIU) by supercooling the sample at 2 °C. In the absence of SSS, the crystallization process was driven by low‐melting‐point triacylglycerols (TAG) such as OSS and OOS (O, oleic; S, stearic acid). There were no differences observed in the crystallinity in the sample based on the solid fat content (P > 0.05) along with any microstructural differences. In addition, an increase in the enthalpy of melting was observed upon sonication, indicating higher crystallinity (P < 0.05). Stronger intramolecular forces were formed in the sonicated samples as evidenced by increased viscoelastic parameters such as the elastic modulus (G′) and storage modulus (G″) (P < 0.05). G′ values increased from 138.25 ± 41.30 to 939.73 ± 277.45 Pa while the G″ values increased from 39.15 ± 8.98 to 149.77 ± 16.00 Pa (P < 0.05). Change in viscosity was not observed as a consequence of sonication (P > 0.05). This study showed that HIU was effective in changing the crystallization behavior of SSS‐free fats with low‐melting TAG.     

Effect of High‐Intensity Ultrasound on the Crystallization Behavior of High‐Stearic High‐Oleic Sunflower Oil Soft Stearin

The objective of this research was to evaluate the effect of high‐intensity ultrasound (HIU) and crystallization temperature (T_c) on the crystallization behavior, melting profile, and elasticity of a soft stearin fraction of high‐stearic high‐oleic sunflower oil. Results showed that HIU can be used to induce and increase the rate of crystallization of the soft stearin with significantly higher SFC values obtained in the sonicated samples, especially at higher T_c. SFC values were fitted using the Avrami model, and higher k_n and lower n values were obtained when samples were crystallized with sonication, suggesting that sonicated samples crystallized faster and through an instantaneous nucleation mechanism. In addition, the crystal morphology, melting behavior, and viscoelasticity were significantly affected by sonication.     

Relationship between oil binding capacity and physical properties of interesterified soybean oil

The objective of this study was to identify the physical properties of an interesterified soybean oil (EIESOY), containing 45% saturated fatty acids (SFA), that correlates with high oil binding capacity (OBC) and low oil loss (OL). In this study, three EIESOY samples were analyzed; a 100% sample, a 50% sample diluted with 50% soybean oil, and a 20% sample diluted with 80% soybean oil. All samples were crystallized using fast (7.78°C/min) and slow (0.1°C/min) cooling rates as well as with and without high-intensity ultrasound (HIU, 20 kHz). The 100%, 50%, and 20% samples were crystallized at 38.5, 27.0, and 22.0°C, respectively. HIU was applied at the onset of crystallization and all samples were allowed to crystallize isothermally for 90 min. After 90 min, physical properties such as crystal microstructure, hardness, solid fat content (SFC), elasticity, and melting behavior were evaluated. Physical properties were also measured after storage for 48 h at 22 and 5°C. Results show that OBC was positively correlated with hardness, G′, and SFC after 48 h (r = 0.738, p = 0.006; r = 0.639, p = 0.025; r = 0.695, p = 0.012; respectively), OL was negatively correlated with hardness after 48 h (r = −0.696, p < 0.001), G′ after 90 min and 48 h (r = −0.704, p < 0.001; r = −0.590, p = 0.002), and SFC after 90 min and 48 h (r = −0.722, p < 0.001; r = −0.788, p < 0.001). Neither OBC nor OL were correlated with crystal diameter or the number of crystals.     

Effects of Ultrasonic Parameters on the Crystallization Behavior of Palm Oil

The crystallization behavior of palm oil (PO) without and with the application of high-intensity ultrasound (HIU) was investigated as the function of irradiation time (20, 60, 120, and 240 s), ultrasonic intensity (47.5, 95, 270, and 475 W) and temperature (20, 25, 30, and 36 °C). The effects on the crystallization behavior of PO were evaluated by ultraviolet/visible spectrophotometry, pulsed nuclear magnetic resonance and polarized light microscopy. Results indicated that all these parameters affected crystallization behavior. HIU significantly reduced the induction time and accelerated the crystallization rate at operating temperatures above 25 °C, but there was no significant difference at 20 °C due to high supercooling. The effects of HIU were more significant at higher power level and longer irradiation time, however, the thermal effect of ultrasound also increased with longer sonication time. The optimal sonication time was approximately 120 s which accelerated the crystallization rate of PO the most. The morphology studies suggested that HIU changed the growth mechanisms of crystals and generated smaller and uniformly crystals. At 36 °C, with extremely low supercooling condition, a combined effect was observed that prevented the separation of solid phase and liquid phase of the crystallized sample, and then led to a uniform distribution of crystals.     

Application of High Intensity Ultrasound to a Zero-trans Shortening During Temperature Cycling at Different Cooling Rates

The objective of this work was to evaluate the effect of high intensity ultrasound (HIU) on the physical properties of a commercial shortening crystallized at a constant temperature and during temperature cycling at two different cooling rates (0.5 and 1 °C/min). Different ultrasound power levels and different durations were evaluated during crystallization at a constant temperature and the best conditions were used to evaluate the effect of HIU during temperature cycling. The physical properties tested were crystal microstructure, viscoelasticity, and melting profile. Results show that HIU is more efficient at changing crystal microstructure when used at 20 °C using a 1/2″ tip. No difference was found on the microstructure of the crystals formed when different durations of ultrasound exposure were tested. A significant increase (p < 0.05) was observed in the storage modulus (G′) of the lipid exposed to temperature fluctuations with the use of HIU. The G′ values increased from 662.6 ± 176.8 Pa (no HIU applied) to 3,365.5 ± 426.4 Pa (with HIU applied, 0.5 °C/min) and from 354.4 ± 49.7 Pa (no HIU applied) to 1,249.0 ± 19.8 Pa (with HIU applied, 1 °C/min).     

Structure and properties of polypentenamer

Trans-1,5-polypentenamer (TPP) has some similarity to natural rubber partly because of properties that relate to crystallinity and to the position of the crystalline melting point. This similarity makes TPP a unique rubber among other synthetic hydrocarbon polymers. Requirements for attaining a good balance of physical properties include adjustment of both micro and macrostructure with processability. Natta, Dall'Asta, Haas and Pampus have described the preparation of polypentenamers based on tungsten or molybdenum catalysts. Since Eleuterio made his disclosure, there have been many important contributions disclosing special conditions for preparing TPP or variations in catalyst preparation including many catalyst activators. Natta and Dall'Asta vulcanized both the TPP and the amorphous cis-1,5-polypentenamer (CPP). They showed that TPP (melting point 23°C) gives good tensile properties even in pure gum vulcanizates characteristic of rubbers that crystallize on stretching. CPP gave better low-temperature characteristics than other hydrocarbon elastomers (SBR rubber, propylene oxide/allyl glycidyl ether copolymer, cis-1,4-polybutadiene). For example, the CPP vulcanizates were less brittle down to ?90°C measured by 100 per cent moduli and, in a comparison of temperatures at which retraction occurred, CPP showed a superiority. With CPP from 25°C to ?70°C, both tensile strengths and moduli increased without appreciable variation of elongation at break. Since the crystalline melting point at rest is near 20°C for TPP, the elastic behavior is governed by this transition rather than the glass transition point (?90°C). The rate of crystallization for TPP is more rapid compared to natural rubber. Although vulcanization is a factor on elastic behavior, we suggest that further compromise may be necessary to balance the desirable properties related to crystallinity while maintaining elasticity at lower temperatures. The summary of the Haas paper noted that TPP rubber is outstanding except that the abrasion, wet skid and heat build-up are inferior to existing tread rubber types. Our efforts suggest that TPP is not inferior. In our examination of TPP's having varied or lowered melting points, vulcanizates (tread recipes) with good low temperature flexibility were developed from TPP with T_m of 5°C. Since tack and green strength are dependent on both the micro and macrostructure, properties lost by decreasing the trans content or the T_m were offset by increasing the molecular weight. With higher molecular-weight TPP, other properties such as heat build-up and abrasion were improved or made equivalent to other tire rubbers. Thus, by optimizing molecular weight, oil level and processability with the microstructure, a good balance of properties may be produced for TPP rubber.     

Sonocrystallization of Interesterified Fats with 20 and 30% of Stearic Acid at the sn-2 Position and Their Physical Blends

Physical blends (PB) of high oleic sunflower oil and tristearin with 20 and 30% stearic acid and their interesterified (IE) products where 20 and 30% of the fatty acids are stearic acid at the sn-2 position crystallized without and with application of high intensity ultrasound (HIU). IE samples were crystallized at supercooling temperatures (ΔT) of 12, 9, 6, and 3 °C while PB were crystallized at ΔT = 12 °C. HIU induced crystallization in PB samples, but not in the IE ones. Induction in crystallization with HIU was also observed at ΔT = 6 and 3 °C for IE C18:0 20 and 30% and at ΔT = 9 °C only for the 30% samples. Smaller crystals were obtained in all sonicated samples. Melting profiles showed that HIU induced crystallization of low melting triacylglycerols (TAGs) and promoted co-crystallization of low and high melting TAGs. In general, HIU significantly changed the viscosity, G′, and G″ of the IE 20% samples except at ΔT = 12 °C. While G′ and G″ of IE 30% did not increase significantly, the viscosity increased significantly at ΔT = 9, 6, and 3 °C from 1526 ± 880 to 6818 ± 901 Pa.s at ΔT = 3 °C. The improved physical properties of the sonicated IE can make them good contenders for trans-fatty acids replacers.     

Chemical and Enzymatic Interesterification of a Blend of Palm Stearin: Soybean Oil for Low trans-Margarine Formulation

A blend of palm stearin and soybean oil (70/30, wt%) was modified by chemical interesterification (CIE) and enzymatic interesterification (EIE), the latter batch-wise (B-EIE) and in continuous (C-EIE). Better oil quality, mainly in terms of acidity, free tocopherol and partial acylglycerol content, was obtained after EIE. The clear melting point after any interesterification process was similar and about 9 °C lower as result of the modification in the TAG profile, which approaches the calculated random distribution. Interesterification changed the SFC profile significantly. For the fully refined interesterified blends, the SFC profile was similar and clearly different from the starting blend. Interesterification decreased the content of solids at temperatures >15 °C and increased the content of solids at temperatures <15 °C. This increase was less remarkable after C-EIE, suggesting that full randomization was not achieved in the used conditions, probably caused by a too short residence time of the oil in the enzymatic bed. During B-EIE, variations in SFC with time, principally at low temperatures, were still observed although the TAG composition was stable. At low temperatures, the reaction rate calculated from SFC was very low, confirming an important effect of the acyl migration on this parameter.     

Sonocrystallization of a Palm-Based Fat with Low Level of Saturation in a Scraped Surface Heat Exchanger

Physical properties of fats are affected by the reduction of saturated fatty acids. One method for retaining desired properties is the use of high-intensity ultrasound (HIU). The aim of this study was to investigate the influence of HIU power levels, pulse time, and position on the physical properties of a low-saturated palm-based fat crystallized in a scraped surface heat exchanger (SSHE). The sample was crystallized in a SSHE at 26 °C, using a 11 L hour⁻¹ flow rate, and agitation of 344 rpm in the barrels and 208 rpm in the pin worker. HIU was applied using a 12.7 mm tip coupled to a water jacketed (26 °C) flow cell that was placed at the end of the SSHE process. Sonication conditions were 20%, 50%, or 80% amplitude using pulses (5 and 10 s) or continuous sonication. After choosing the best HIU condition, the position of the flow cell was changed to different positions within the SSHE: before the first barrel (HIU-0), between the two barrels (HIU-1), between the second barrel and the pin worker (HIU-2), and after the pin worker (HIU-3). The best sonication condition from the first set of experiments was when HIU was applied using 50% amplitude and 10 s pulses. This condition resulted in higher oil binding capacity (OBC) and storage modulus (G') compared to the non-sonicated sample (OBC: 77% against 69.5%; G':154 kPa against 108 kPa). The best HIU position was HIU-3 since no further agitation was applied. The lack of agitation after sonication induced secondary nucleation and generated a strong crystalline network.     

Melt miscibility in blends of polypropylene,polystyrene-block-poly(ethylene-stat-butylene)-block-polystyrene,and processing oil from melting point depression

The miscibility of isotactic polypropylene (PP) in blends with (a) polystyrene-block-poly(ethylene-stat-butylene)-block-polystyrene (SEBS) and processing oil, (b) poly(ethylene-co-propylene) (EPM), and (c) EPM and processing oil, has been studied using the method of melting-point depression. Near equilibrium melting temperatures were determined by applying the Hoffman-Weeks method to PP melting temperatures determined by DSC on samples crystallized isothermally for 20 h at 80, 100, 120 and 140°C. A large melting point depression was observed for PP in blends with SEBS and processing oil, suggesting that PP was soluble in the molten blends. On melting, the turbidity of the PP/SEBS/Oil blends increased, suggesting that the equilibrium melt contains two liquid phases. For PP in blends with EPM or EPM and processing oil, a melting-point depression was not observed. The results indicate why PP/SEBS/Oil blends, within a wide composition range, formed bicontinuous interpenetrating network structures on cooling from the melt, whereas all of the blends with EPM formed solid blends with one continuous phase and one dispersed phase.     

Physical State of β‐Carotene at High Concentrations in a Solid Triglyceride Matrix

The highly hydrophobic β‐carotene is often distributed or dissolved in triglycerides to enhance either nutritional or coloring effects. This study aims at elucidating the physical state of β‐carotene that at high concentrations are mixed into a solid high‐melting tri‐glyceride matrix by dissolution at high temperatures (165 °C) in the melted triglyceride. Extensive isomerization of β‐carotene is observed by HPLC after melting crystalline all‐trans β‐carotene and in the solid mixtures of β‐carotene and fully hydrogenated sunflower oil. Crystalline triglyceride is found in the mixed samples by XRPD analysis whereas no signs of crystalline lattice structures of β‐carotene are detected. DSC thermograms show only the melting and recrystallization events of triglycerides, which are affected by the presence of β‐carotene. Severe line broadening is observed in the ¹³C CP/MAS NMR spectra of the β‐carotene‐triglyceride mixtures when compared to crystalline β‐carotene, demonstrating the lack of long‐range order of the carotene. Altogether, the results demonstrate that β‐carotene is present as an amorphous mixture of trans‐ and cis‐isomers dispersed into a structure of crystalline triglyceride in the solid carotene‐triglyceride mixtures. Practical applications: The amorphous structure of trans‐ and cis‐isomers in solid formulations of β‐carotene‐triglyceride mixtures will strongly affect their functional properties related to nutrition and color as food ingredients.     

Study of the morphology of poly(butylene succinate)/poly(ethylene oxide) blends using hot-stage atomic force microscopy

Blends of poly(butylene succinate) (PBS) and poly(ethylene oxide) (PEO) were cast into films, melted, and crystallized. A number of PBS/PEO blend compositions, ranging from 85/15 to 20/80 were used. The PBS, with a higher melting point, always crystallizes first, providing a scaffold on which the PEO would crystallize. AFM phase and height images were made at room temperature and at higher temperatures, as the PEO melted, allowing one to determine the morphology and location of the PEO. It was found that at low PEO concentrations (below 15 w/o) the PEO resides preferentially between PBS lamellae. This interlamellar PEO does not crystallize, except under extreme undercooling. At higher concentrations, larger amorphous domains exist within the PBS crystalline scaffold and PEO can crystallize in these domains. Two unexpected phenomena are observed: (1) the reversible exuding of PEO from interlamellar spaces to the surface for crystallization and (2) an unusual orientation of PEO lamellae within amorphous domains in the PBS scaffold.     

Morphology,crystallization and melting properties of isotactic polypropylene blended with lignin

The influence of lignin (L) on the thermal properties and kinetics of crystallization of isotactic polypropylene (PP) is reported in this article. PP blends containing 5 and 15 wt % of L were prepared by mixing the components in a screw mixer. An increase of the thermal degradation temperature of the blends was observed as a function of L content. The crystallization and thermal behavior of the pure PP and of the PP/L blends were analyzed by differential scanning calorimetry (DSC). Isothermal crystallization kinetics were described by means of the Avrami equation, which suggests a three‐dimensional growth of crystalline units, developed by heterogeneous nucleation. The isothermal growth rate of PP spherulites was studied using a polarizing optical microscope. The enhancement of PP crystallization rate for the PP/L blends was observed and ascribed to the nucleating action of lignin particles. Non‐isothermal crystallization kinetics were applied, according to the results elaborated by Ziabicki and the method modified by Jeziorny. The kinetic crystallizability of the PP is not influenced by the L present in the blend. In the presence of L, PP can simultaneously crystallize in both the α and β crystalline forms, and the ratio between the α and β forms was determined by X‐ray diffraction analysis. Two melting peaks relative to the two crystalline form of PP were observed for the PP/L blends, for all isothermal crystallization temperatures investigated by means of DSC. The equilibrium melting temperature for α‐form of pure PP was obtained. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1435–1442, 2004     

Crystallization and melting behavior of blends comprising poly(3‐hydroxy butyrate‐co‐3‐hydroxy valerate) and poly(ethylene oxide)

Blends of poly(3‐hydroxy butyrate‐co‐3‐hydroxy valerate) (PHBV) and poly(ethylene oxide) (PEO) were prepared by casting from chloroform solutions. Crystallization kinetics and melting behavior of blends have been studied by differential scanning calorimetry and optical polarizing microscopy. Experimental results reveal that the constituents are miscible in the amorphous state. They form separated crystal structures in the solid state. Crystallization behavior of the blends was studied under isothermal and nonisothermal conditions. Owing to the large difference in melting temperatures, the constituents crystallize consecutively in blends; however, the process is affected by the respective second component. PHBV crystallizes from the amorphous mixture of the constituents, at temperatures where the PEO remains in the molten state. PEO, on the other hand, is surrounded during its crystallization process by crystalline PHBV regions. The degree of crystallinity in the blends stays constant for PHBV and decreases slightly for PEO, with ascending PHBV content. The rate of crystallization of PHBV decreases in blends as compared to the neat polymer. The opposite behavior is observed for PEO. Nonisothermal crystallization is discussed in terms of a quasi‐isothermal approach. Qualitatively, the results show the same tendencies as under isothermal conditions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2776–2783, 2006     

Viscosity index. III. Thermodynamic parameters for side chain crystallinity in pour point-modified blends containing n-octadecyl acrylate

The melting transitions and heats of fusion were obtained by differential scanning calorimetry for the crystalline phase of the same mixtures whose rheological properties were reported in the previous two papers. Pour point temperatures were also determined. In addition, the same thermodynamic quantities were also collected for higher polymer concentrations in this work, thus encompassing the entire concentration range. The DSC scans revealed that the distribution of crystallite sizes characteristic of the bulk copolymers was retained in the blends. Phase diagrams indicated isomorphism in all systems studied. An equation was derived to predict the influence of diluent concentration on melting point depression of copolymers, in which one component crystallizes through its side chains but in which the side chains of the other remain amorphous. The difference between the experimental heats of fusion and the value for entirely crystalline poly(n-octadecyl acrylate) were used to estimate extent of apparent cocrystallization of the different copolymers with the base oil. While this tended to increase with pour point-depressant ability, concomitant crystallinity of wax and depressant were essential to successful wax crystal modification. A mechanism is proposed in which whole molecules of hexagonally packed copolymers are attached to wax nuclei and accumulate slowly a t low diffusion rates. Thus, growth occurs over small crystal areas and is considered responsible for the directing influence of copolymer depressant. The resulting small crystal sizes, accompanied by fast growth of rapidly diffusing paraffins on uncontaminated surfaces, promote more compact habits, like dendrites that postpone network formation to lower temperatures. It was concluded that a melting point difference of less than 25°C between bulk copolymer and base oil is required for successful pour point depression. Consequently, in this base oil, only copolymers with long amorphous side chains in a limited composition range, such as the n-octadecyl acrylate–2-ethylhexyl acrylate copolymers, possessed sufficient lattice disorder to meet the specification. The rest produced gelation at higher temperatures.     

Some physical properties of castor oil esters and hydrogenated castor oil esters

Esters of castor oil and hydrogenated castor oil were prepared with C₆, C₁₂, C₁₆, C₁₈ fatty acids, using tetra‐n‐butyl titanate as a catalyst and n‐butyl benzene as a water entrainer. Physical properties such as melting point, refractive index, viscosity, and specific gravity of these esters were measured. Slip melting points of the esters were very low in both cases. These esters did not crystallize even at low temperature. The highest slip melting point obtained was 21 °C with stearoyl hydrogenated castor oil ester and lowest slip melting point obtained was —6 °C with hexanoyl castor oil ester.     

Single crystals of crystalline block copolymers formed in n‐hexanol and methanol/DMF solutions: A comparative study

Lamellar single crystals of poly(?‐caprolactone) (PCL)‐based crystalline/liquid‐crystalline block copolymer (BCP) were prepared from two methods: solution crystallization in n ‐hexanol as well as addition of methanol dropwise to BCP/DMF solution. The crystalline morphologies of PCL single crystals prepared at different temperatures were investigated. It was observed that well‐developed single crystals were formed in n ‐hexanol at high crystallization temperatures, while low crystallization temperatures favored to fabricate well‐developed nanosheets in methanol/DMF. Annealing at the melting temperature of single crystals yielded the crystalline seeds and unimers in n ‐hexanol, while it formed spherical micelles in methanol/DMF system. As a result, the size of single crystals in n ‐hexanol could be tuned by addition of different ratios of unimer/seed. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45089.