Cocrystallization mechanism of poly(3-alkyl thiophenes) with different alkyl chain length

The crystallization rates of poly(3-alkyl thiophene) (P3AT) cocrystals having different alkyl chain length (e.g. hexyl and octyl) of the components are measured using differential scanning calorimetry (DSC) technique. Two pairs of cocrystals with varying compositions of the components viz. poly(3-octyl thiophene) (P3OT(R), regioregularity 89 mol%) and poly(3-hexyl thiophene) [P3HT(R), regioregularity 92 mol% and P3HT-2 regioregularity 82 mol%] are used. In both the systems the isothermal temperature range (TR) in the same time scale of crystallization is found to decrease with increasing alkyl chain length in the blends. The crystallization rate at the same T_c decreases with increasing alkyl chain length P3AT concentration and the Avrami exponent values of cocrystals are same with those of the component values. The low Avrami exponent values (0.23-1.16) in all the samples suggest the presence of rigid amorphous portion which can not diffuse out quickly from the crystal growth front (soft impingement). Analysis of crystallization rate using Laurintzen-Hoffman (L-H) growth rate theory indicates that there is regime-I to regime-II transition in all the samples. The product of lateral (σ) and end surface energy (σ_e) values are found to decrease with increasing the concentration of longer alkyl chain P3AT in the blend. Analysis of σ values according to a theory of Hoffman et al. [Hoffman JD, Miller RL, Marand H, Rotiman DR. Macromolecules 1992;25:2221. [14]] indicates that there is chain extension of the components in the melt of the blends, however, the entropy of cocrystallization has different sign to the two systems. Cocrystallization in P3HT(R)/P3OT(R) system is an entropy driven process but that in P3HT(2)/P3OT(R) system is entropy forbidden process. A possible explanation of cocrystallization in the later system has been attributed from small interaction between the components.     

Effect of the regioregularity of poly(3‐hexylthiophene) on the performances of organic photovoltaic devices

BACKGROUND: The highest efficiencies of bulk‐heterojunction solar cells from poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM) reported so far are close to 6%. Phenomena occurring during the photovoltaic process, such as the creation, diffusion and separation of excitons, as well as charge carrier transport, are governed by the active layer morphology. The latter phenomenon, which depends on the self‐organization of P3HT, can be influenced by its degree of regioregularity. The aim of this work is to clarify the relationship between the regioregularity of P3HT, the composition of P3HT/PCBM blends and the performances of photovoltaic devices. RESULTS: Two types of P3HTs with different degrees of regioregularity have been synthesized and used as active layers with PCBM in photovoltaic cells. The higher performances in photovoltaic devices are obtained for high‐regioregular P3HT and can be explained considering the self‐organizing properties of high‐regioregular P3HT, leading to higher sunlight absorption and higher hole mobilities. In addition, this report demonstrates the importance of the ratio of P3HT versus PCBM in correlation with the regioregularity of P3HT on the optical properties, charge transport and characteristics of photovoltaic cells. CONCLUSION: We have investigated the dependence of the photovoltaic properties of P3HT/PCBM blend‐based photovoltaic devices on the degree of regioregularity of P3HT. We find that the best performance is exhibited by devices based on highly regioregular P3HT. Also, the best performances are not obtained for the same P3HT:PCBM weight ratios for high‐regioregular P3HT (1:0.8) and low‐regioregular P3HT (1:3). Copyright © 2007 Society of Chemical Industry     

Influence of alkyl chain length on the gelation mechanism of thermoreversible gels of regioregular poly(3‐alkyl thiophenes) in xylene

The gelation rates of poly(3‐alkyl thiophenes) (P3AT) are strongly dependent on the pendent alkyl chain length. Poly(3‐hexyl thiophene (P3HT) gels at higher isothermal temperatures than that of poly(3‐dodecyl thiophene), (P3DDT). Gelation rate has been expressed as a combination of a temperature dependent function f(T) and a concentration dependent function (φⁿ); φ being the reduced overlapping concentration of P3AT. From the slope of double logarithmic plot of gelation rate and φ, n values are calculated to be 0.52 and 0.60 for P3HT and P3DDT, respectively. These values are close to the value of percolation exponent β (0.45) for three‐dimensional lattice; so both the gels may approximately obey three dimensional percolation model. The f(T) of gelation rate consists of two steps (i) coil‐to‐rod transformation followed by (ii) fibrillar crystallization. The coil‐to‐rod transition is accompanied by a red shift in the π–π* transition band in UV–vis spectra. Flory and Weaver theory is used to understand the coil‐to‐rod transformation process. The theory of fibrillar crystallization extended to dilute solution has been employed to understand the crystallization process. The results clearly indicate that the activation energy of conformational change (ΔF) is higher for P3DDT than that of P3HT. But the free energy change for the formation of critical size nucleus (Δ G) is lower for P3DDT than that of P3HT. A comparison of ΔF and Δ G values indicate conformational ordering is the rate‐determining step for P3AT with dodecyl substituent whereas crystallization is the rate‐determining step for P3AT with hexyl substituent. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2528–2537, 2007     

Butterfly nanostructures via regioregularly grafted multi‐walled carbon nanotubes and poly(3‐hexylthiophene) to improve photovoltaic characteristics

Butterfly nanostructures were designed using multi‐walled carbon nanotubes (CNTs) grafted with regioregular poly(3‐hexylthiophene) (RR‐P3HT) chains (CNT‐graft‐P3HT). The secondary crystallization of RR‐P3HT free chains onto CNT‐graft‐P3HT reflected the donor–acceptor supramolecules with a butterfly configuration, in which the CNT acted as the body of the butterfly and seeded crystallization of P3HT free chains resulted in the wings having a width of 37–38 nm. Butterfly supramolecules demonstrated high melting point (241.2 °C), fusion enthalpy (31.5 J g^?1) and crystallinity (85.13%). High photoluminescence quenching and thus donating–accepting property were also detected for the butterfly nanohybrids with a bandgap energy of 1.94 eV. Incorporation of butterfly nanostructures in the active layer of photovoltaic devices (P3HT:butterfly) conspicuously affected the system characteristics including short circuit current density (J_sc; 10.84 mA cm^?2), fill factor (FF; 56%) and power conversion efficiency (PCE; 3.94%). The inclusion of phenyl‐C71‐butyric acid methyl ester molecules as second acceptor in thin‐film active layers further increased the efficacy of systems, i.e. J_sc of 12.23 mA cm^?2, FF of 63%, open circuit voltage of 0.66 V and PCE of 5.08%, without considering external treatments and additives. © 2018 Society of Chemical Industry     

Efficiency above 6% in poly(3‐hexylthiophene):phenyl‐C‐butyric acid methyl ester photovoltaics via simultaneous addition of poly(3‐hexylthiophene) based grafted graphene nanosheets and hydrophobic block copolymers

A combination of reduced graphene oxide (rGO) nanosheets grafted with regioregular poly(3‐hexylthiophene) (P3HT) (rGO‐g‐P3HT) and P3HT‐b‐polystyrene (PS) block copolymers was utilized to modify the morphology of P3HT:[6,6]‐phenyl‐C71‐butyric acid methyl ester (PC71BM) active layers in photovoltaic devices. Efficiencies greater than 6% were acquired after a mild thermal annealing. To this end, the assembling of P3HT homopolymers and P3HT‐b‐PS block copolymers onto rGO‐g‐P3HT nanosheets was investigated, showing that the copolymers were assembled from the P3HT side onto the rGO‐g‐P3HT nanosheets. Assembling of P3HT‐b‐PS block copolymers onto the rGO‐g‐P3HT nanosheets developed the net hole and electron highways for charge transport, thereby in addition to photoluminescence quenching the charge mobility (μ_h and μ_e) values increased considerably. The best charge mobilities were acquired for the P3HT₅₀₀₀₀:PC71BM:rGO‐g‐P3HT₅₀₀₀₀:P3HT₇₀₀₀‐b‐PS₁₀₀₀ system (μ_h = 1.9 × 10^?5 cm² V^–1 s^–1 and μ_e = 0.8 × 10^?4 cm² V^–1 s^–1). Thermal annealing conducted at 120 °C also further increased the hole and electron mobilities to 9.8 × 10^?4 and 2.7 × 10^?3 cm² V^–1 s^–1, respectively. The thermal annealing acted as a driving force for better assembly of the P3HT‐b‐PS copolymers onto the rGO‐g‐P3HT nanosheets. This phenomenon improved the short circuit current density, fill factor, open circuit voltage and power conversion efficiency parameters from 11.13 mA cm^?2, 0.63 V, 62% and 4.35% to 12.98 mA cm^?2, 0.69 V, 68% and 6.09%, respectively. © 2019 Society of Chemical Industry     

Sequence analysis and fiber properties of a blend of poly(ethylene terephthalate) and poly(ethylene terephthalate‐co‐4,4′‐bibenzoate)

Blends of poly(ethylene terephthalate) (PET) and poly(ethylene terephthalate‐co‐4,4′‐ bibenzoate) (PETBB) are prepared by coextrusion. Analysis by ¹³C‐NMR spectroscopy shows that little transesterification occurs during the blending process. Additional heat treatment of the blend leads to more transesterification and a corresponding increase in the degree of randomness, R. Analysis by differential scanning calorimetry shows that the as‐extruded blend is semicrystalline, unlike PETBB15, a random copolymer with the same composition as the non‐ random blend. Additional heat treatment of the blend leads to a decrease in the melting point, T_m, and an increase in glass transition temperature, T_g. The T_m and T_g of the blend reach minimum and maximum values, respectively, after 15 min at 270°C, at which point the blend has not been fully randomized. The blend has a lower crystallization rate than PET and PETBB55 (a copolymer containing 55 mol % bibenzoate). The PET/PETBB55 (70/30 w/w) blend shows a secondary endothermic peak at 15°C above an isothermal crystallization temperature. The secondary peak was confirmed to be the melting of small and/or imperfect crystals resulting from secondary crystallization. The blend exhibits the crystal structure of PET. Tensile properties of the fibers prepared from the blend are comparable to those of PET fiber, whereas PETBB55 fibers display higher performance. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1793–1803, 2004     

Isothermal crystallization kinetics in binary miscible blend of poly(ε‐caprolactone)/tetramethyl polycarbonate

The crystallization kinetics of pure poly(ε‐caprolactone) (PCL) and its blends with bisphenol‐A tetramethyl polycarbonate (TMPC) was investigated isothermally as a function of composition and crystallization temperature (T_c) using differential scanning calorimetric (DSC) and polarized optical microscope techniques. Only a single glass‐transition temperature, T_g, was determined for each mixture indicating that this binary blend is miscible over the entire range of composition. The composition dependence of the T_g for this blend was well described by Gordon–Taylor equation with k = 1.8 (higher than unity) indicating strong intermolecular interaction between the two polymer components. The presence of a high T_g amorphous component (TMPC) had a strong influence on the crystallization kinetics of PCL in the blends. A substantial decrease in the crystallization kinetics was observed as the concentration of TMPC rose in the blends. The crystallization half‐time t_0.5 increased monotonically with the crystallization temperature for all composition. At any crystallization temperature (T_c) the t_0.5 of the blends are longer than the corresponding value for pure PCL. This behavior was attributed to the favorable thermodynamics interaction between PCL and TMPC which in turn led to a depression in the equilibrium melting point along with a simultaneous retardation in the crystallization of PC. The isothermal crystallization kinetics was analyzed on the basis of the Avrami equation. Linear behavior was held true for the augmentation of the radii of spherulites with time for all mixtures, regardless of the blend composition. However, the spherulites growth rate decreased exponentially with increasing the concentration of TMPC in the blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3307–3315, 2007     

Reactive blends of polyamide 6 with polyester elastomer using coupling agents

In situ compatibilized melt blends of polyamide 6 (PA‐6) with polyester elastomer (PEL) were prepared in a corotating twin‐screw extruder using two types of coupling agent (CA): diglycidyl ether of bisphenol A (DGEBA) and 1,4‐phenylene bis(2‐oxazoline) (PBO). The notched impact strength of PA‐6 and PA‐6/PEL blends increased with the addition of coupling agent, especially DGEBA, and the maximum impact toughening of the blend was obtained with 0.6 mol % DGEBA, the composition of minimum domain size observed from SEM. Viscosities of the untreated blends increased over those of the base resins at low frequencies. Viscosities of both the base resins and the blends increased with the addition of CA, and the effect was much more pronounced with DGEBA, especially for PA‐6 and PA‐6–rich blends. The crystallization temperature (T_c) of PEL increased over 10°C, whereas the T_c of PA‐6 decreased by 2–3°C in the blends. With the addition of coupling agents, the crystallization melting temperature (T_m) and T_c of PA‐6 decreased by up to 5°C with DGEBA, implying that the crystallization of PA‐6 is disturbed by the in situ formed PA‐6–CA–PEL or PA‐6–CA–PA‐6 type copolymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3966–3973, 2004     

Thermal and crystallinity property studies of poly (L‐lactic acid) blended with oligomers of 3‐hydroxybutyrate or dendrimers of hydroxyalkanoic acids

Poly (L ‐lactic acid) (PLA) is a biodegradable polymer with slow crystallization rate. Oligomers of 3‐hydroxybutyrate (OHB) and dendrimers of hydroxyalkanoic acids with different molecular weights were blended with PLA in a hope to improve the crystallization ability and thermal stability of PLA, respectively. Four thermally‐degraded PHB products oligomers termed OHB‐1, OHB‐2, OHB‐3, and OHB‐4 with various number average molecular weights (M_n) of 4000, 7400, 14,000, and 83,000, respectively, were blended with PLA. The lower cold‐crystallization temperature (T_cc) and higher heat of cold crystallization (ΔH_cc) for blend of PLA/OHB‐1 suggested that thermally‐degraded OHB‐1 formed suitable crystal size during the cooling process and then acted as nucleation agents for PLA in the subsequent heating process. On the other hand, for the blending systems of PLA/dendrimers of hydroxyalkanoic acids, no obvious change on the thermal properties was observed compared with pure PLA except an improved PLA thermal stability possibly resulted from the crosslinking effects of the dendrimers © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Enhanced miscibility and strain resistance of blended elastomer/π‐conjugated polymer composites through side chain functionalization towards stretchable electronics

This work presents improved compatibility in an elastomer/π‐conjugated polymer blend through side chain functionalization of the electronic polymer. Poly[(3‐(6‐bromohexyl)thiophene)‐ran‐(3‐hexylthiophene)] (P3Br_xHT, x = 0%–100%) was synthesized (i) to improve miscibility with polybutadiene (PB) elastomer through altered π–π interactions and (ii) to covalently bond across phase‐segregated interfaces. Functionalization led to morphology with reduced domain sizes to improve crack onset strain from 7% to 40%. Furthermore, UV‐activated crosslinking reinforced mechanically weak interfaces and yielded at least an additional 40% increase in crack onset strain. Charge mobility in PB/P3Br_xHT organic field‐effect transistors showed minimal dependence on bromide concentration and no negative effects from crosslinking. Functionalization was an effective method to reduce brittleness in PB/P3Br_xHT blends through morphology modification and crosslinking to improve stability towards strain for potential stretchable electronic applications. © 2019 Society of Chemical Industry     

Particle size effect on the film‐forming process of PS/PBA composite latexes

In this work, the effect of hard particle size and blend ratio on the film formation behavior of hard polystyrene (PS) and soft poly(n‐butyl acrylate) (PBA) latex blends was studied by means of steady‐state fluorescence and UV–visible techniques in conjunction with atomic force microscopy. Three different sets of latexes were synthesized: PBA latex (diameter 97 nm), pyrene (P)‐labeled large PS (LgPS; diameter 900 nm), and small PS (SmPS; diameter 320 nm). Two different series of latex blends (LgPS/PBA and SmPS/PBA) were prepared with varying blend composition at room temperature separately. Films were then annealed at elevated temperatures above glass transition (T_g) temperature of PS. Fluorescence intensity (I_P) from P and photon transmission intensity (I_tr) were measured after each annealing step to monitor the stages of film formation. The results showed that a significant change occurred in I_P and I_tr at a certain critical weight fraction (R_c) of PBA. Below R_c, two distinct film formation stages, which are named as void closure and interdiffusion, were seen. However, at PBA concentrations nearer to or above R_c, no film formation can be achieved. Comparing to the LgPS/PBA, the sintering process of SmPS/PBA particles occurred at much lower temperatures. Film formation stages for R < R_c were modeled, and related activation energies were calculated. Void closure (ΔH) and interdiffusion (ΔE) activation energies for SmPS/PBA were also found smaller in comparing with LgPS/PBA series. However, ΔH and ΔE values were not changed much with the blend composition for both series. POLYM. COMPOS., 31:1637–1652, 2010. © 2009 Society of Plastics Engineers     

Stereocomplex formation between poly(L‐lactic acid) and poly(D‐lactic acid) with disproportionately low and high molecular weights from the melt

Poly(L ‐lactic acid) (PLLA) and poly(D ‐lactic acid) (PDLA) with very different weight‐average molecular weights (M_w) of 4.0 × 10³ and 7.0 × 10⁵ g mol^?1 (M_w(PDLA)/M_w(PLLA) = 175) were blended at different PDLA weight ratios (X_D = PDLA weight/blend weight) and their crystallization from the melt was investigated. The presence of low molecular weight PLLA facilitated the stereocomplexation and thereby lowered the cold crystallization temperature (T_cc) for non‐isothermal crystallization during heating and elevated the radial growth rate of spherulites (G) for isothermal crystallization, irrespective of X_D. The orientation of lamellae in the spherulites was higher for the neat PLLA, PDLA and an equimolar blend than for the non‐equimolar blends. It was found that the orientation of lamellae in the blends was maintained by the stereocomplex (SC) crystallites. Although the G values are expected to decrease with an increase in X_D or the content of high‐molecular‐weight PDLA with lower chain mobility compared with that of low‐molecular‐weight PLLA, G was highest at X_D = 0.5 where the maximum amount of SC crystallites was formed and the G values were very similar for X_D = 0.4 and X_D = 0.6 with the same enantiomeric excess. This means that the effect of SC crystallites overwhelmed that of chain mobility. The nucleating mechanisms of SC crystallites were identical for X_D = 0.1–0.5 in the T_c range 130–180 °C. Copyright © 2011 Society of Chemical Industry     

Study of the processing pathway for cosolvent addition in active layer preparation of inverted organic solar cell

Investigation on processing pathway for co‐solvent addition in active layer preparation of an inverted organic solar cell indicated that the composite films cast out of simple marginal solvent (like cyclohexanone) addition in poly(3‐hexyl thiophene)‐[6,6]‐phenyl C₆₁‐butyric acid methyl ester (P3HT‐PCBM) solution were not effectively crystallized. A comparison of one step direct marginal solvent addition to the P3HT‐PCBM solution with the modified two step process consisting of primary P3HT crystallization in first step by marginal solvent addition to a solution of only P3HT in good solvent (like ortho‐dichloro benzene) followed by mixing of PCBM solution revealed improvement in P3HT crystallization in the latter method. Grazing incidence X‐ray diffraction measurements supported favorable vertical concentration gradient in the P3HT‐PCBM composite film. This modification of active layer morphology with the two step individually mixed cyclohexanone addition into the active layer spin coating solution results in an improved power conversion efficiency of 3.39%, an improvement of more than 10% compared to the conventional one step blended co‐solvent addition method. POLYM. ENG. SCI., 55:1758–1766, 2015. © 2014 Society of Plastics Engineers     

Isothermal crystallization kinetics and melting behaviors of poly(butylene terephthalate) and poly(butylene terephthalate‐co‐fumarate) copolymer

The isothermal crystallization kinetics and melting behaviors after isothermal crystallization of poly(butylene terephthalate) (PBT) and poly(butylene terephthalate‐co‐fumarate) (PBTF) containing 95/5, 90/10, and 80/20 molar ratios of terephthalic acid/fumaric acid were investigated by differential scanning calorimetry. The equilibrium melting temperatures of these polymers were estimated by Hoffman–Weeks equation. So far as the crystallization kinetics was concerned, the Avrami equation was applied and the values of the exponent n for all these polymers are in the range of 2.50–2.96, indicating that the addition of fumarate does not affect the geometric dimension of PBT crystal growth. Crystallization activation energy (ΔE) and nucleation constant (K_g) of PBTF copolymers are higher than that of PBT homopolymer, suggesting that the introduction of fumarate hinders the crystallization of PBT in PBTF. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Sulfur‐containing polymers: Effect of composition on melting behavior and crystallization kinetics of poly(butylene terephthalate)

The melting behavior and crystallization kinetics of poly(butylene terephthalate/thiodipropionate) (PBT) copolymers were investigated using the differential scanning calorimetry technique. Multiple endotherms typical of PBT were observed in the copolymers under investigation and were found to be influenced both by crystallization temperature (T_c) and composition. Wide‐angle X‐ray diffraction measurements permitted the identification of the crystalline structure of PBT in all the copolymers investigated. By applying the Hoffman–Weeks method, the equilibrium melting temperature of the copolymers was derived. Isothermal crystallization kinetics were analyzed according to Avrami's treatment. Values of the exponent n close to 3 were obtained, independent of T_c and composition, results in agreement with it being a crystallization process originating from predetermined nuclei and characterized by three‐dimensional spherulitic growth. The introduction of butylene thiodipropionate units was found to decrease the PBT crystallization rate. The heat of fusion (ΔH_m) was correlated to the specific heat increment (Δc_p) of samples of different degrees of crystallinity, and the results were interpreted based on there being an interphase, whose amount was found to increase as the sulfur‐containing unit content was increased. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2003–2009, 2003     

A novel electrochemically and thermally stable polythiophene for photovoltaic application

Conjugated polymers having good electrochemical and thermal stability are highly desired in optoelectronics. We report a new polythiophene consisting of alternating 4,4′‐didodecyl‐2,2′‐bithiophene and terthiophene units (HPL1) synthesized via Stille coupling reaction. The optical band gap of HPL1 (1.92 eV) is similar to that of regioregular poly(3‐hexylthiophene) (rr‐P3HT, 1.89 eV). In comparison to rr‐P3HT, the HPL1 when subjected to the cyclic voltammetry as thin film shows much superior electrochemical stability and a lower highest occupied molecular orbital energy level (?4.87 eV for rr‐P3HT and ?4.95 eV for HPL1). The transient photoluminescence study of HPL1 and rr‐P3HT shows that both materials have two exciton decay processes, and the excitons of rr‐P3HT are quenched more quickly. The onset decomposition, T_d for rr‐P3HT (465°C) is 4°C lower than HPL1 (469°C). Preliminary photovoltaic study disclosed that the polymer solar cell based on HPL1:[6,6]‐phenyl‐C₆₁‐butyric acid methyl ester blend showed a power conversion efficiency of 0.63%, with a V_oc of 0.6 V, and a short circuit current (J_sc) of 2.79 mA cm^?2 under AM 1.5 illumination (100 mW cm^?2). The whole study provided an important example to design new electrochemically and thermally stable polymers with longer exciton life time for application in bulk heterojunction polymer solar cells. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Physical properties of palm‐based diacylglycerol and palm‐based oils in the preparation of shelf‐stable margarine

Ternary mixtures containing palm olein (POL), palm kernel oil (PKO) and palm oil‐based diacylglycerol (PO‐DAG) were designed using mixture design. The corresponding physical properties such as solid fat content (SFC) as well as deviation from SFC (ΔSFC) using nuclear magnetic resonance (NMR) and melting and crystallization properties using differential scanning calorimetry (DSC) were studied. Ternary phase behaviour was analysed using isosolid diagrams. The most intensive eutectic interaction among the three binary blends studied was observed along the binary line of PKO/PO‐DAG followed by POL/PKO and POL/PO‐DAG. The higher ΔSFC did not always lead to the more intensive eutectic behaviour among the blends. Addition of pure POL, 33.33 and 66.66% POL, and no POL to 50/50 mixture of PKO/PO‐DAG decreased heat of crystallization (ΔHc) as well as crystallization onset (T_O). However, as the same amounts of PO‐DAG and PKO were added to the 50/50 mixtures of POL/PKO and POL/PO‐DAG, respectively, blend containing the equi‐mixture of POL, PKO and PO‐DAG (33.33/33.33/33.33) was found to have the lowest ΔHc. This was also reflected in the corresponding eutectic effect observed at 20–25 and 5–10°C, respectively. Palm‐based DAG‐enriched shelf‐stable margarine consisting of POL/PKO/PO‐DAG (42.5/42.5/15 w/w) was optimally formulated through analysis of multiple isosolid diagrams and was found to have quite similar SFC profile with commercial shelf‐stable margarine. Practical applications: In this study, valuable information about complicated interactions among the palm oil‐based diacylglycerol (PO‐DAG) and palm‐based oils with different FA chain length was obtained in the ternary system. These informative data may be useful in future exploitation of solid fat‐based DAG in blend with natural fats for various DAG‐enriched plastic fat products. Furthermore, Design Expert software was found to be a valuable tool to optimize the new fat blend formulation using the minimum number of blend preparation. By using this tool, assessment of complicated behaviour among the blend components through construction of the corresponding phase diagrams which are critical for optimization purposes as well as fat product development, would also be possible.     

Thermal analysis and non‐isothermal kinetics of poly(ethylene glycol) with different molecular weight

This study focuses on comprehensively investigating polyethylene glycol (PEG) with different molecular weight. Thermal properties of the PEGs were investigated by differential scanning calorimetry (DSC), as well as gradual melting and freezing tests with thermocouples. Results show that the degree of PEG crystallization increased with the increasing of the molecular weight of polymers. The temperatures of pure PEG 1000 and PEG 1000‐PEG 600 blends ranged from 20 to 50°C. The apparent activation energy of pure PEG1000 was 300 kJ/mol, whereas that of the PEG blend was 239 kJ/mol. During the crystallization process, Avrami index n ranged from 5 to 3 and half‐crystallization time t_1/2 decreased with the acceleration of the crystallization rate R. This difference was due to the increase in polydispersity of the PEG system and decrease in the degree of crystallization. POLYM. ENG. SCI., 54:2872–2876, 2014. © 2014 Society of Plastics Engineers     

Crystallization kinetics of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) blends

The crystallization kinetics of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) (PET/PEN) blends were investigated by DSC as functions of crystallization temperature, blend composition, and PET and PEN source. Isothermal crystallization kinetics were evaluated in terms of the Avrami equation. The Avrami exponent (n) is different for PET, PEN, and the blends, indicating different crystallization mechanisms occurring in blends than those in pure PET and PEN. Activation energies of crystallization were calculated from the rate constants, using an Arrhenius‐type expression. Regime theory was used to elucidate the crystallization course of PET/PEN blends as well as that of unblended PET and PEN. The transition from regime II to regime III was clearly observed for each blend sample as the crystallization temperature was decreased. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 23–37, 2001     

Elastic behavior of LDPE/HEPE blend melts in capillary extrusion

The studies of the elastic behavior in the capillary flow of LDPE/HDPE blend melts were carried out at a test temperature range from 180 to 200°C and at an apparent shear rate of about 25–120 s⁻¹. The end‐pressure drop (ΔP_end) increased nonlinearly with increasing wall shear stress (τ_w) and achieved a minimum value at a weight fraction (ϕ_HD) of HDPE of 50%. The die‐swell ratio (B) increased basically linearly with increasing τ_w or ΔP_end and achieved a maximum value at ϕ_HD of 50%. With the addition of the die length–diameter ratio, the values of B were decreased linearly. At a low shear rate, the temperature sensitivity of the melt die‐swell was more significant than at a high shear rate. With increasing ϕ_HD, B increased when ϕ_HD < 50%, then decreased. B reached a maximum value at ϕ_HD of 50% and a fixed apparent shear rate. This phenomenon may be explained by using the theory of viscoelastic competition between components of polymer blend melts. Furthermore, the first normal stress difference (N₁) of the sample melts was estimated by using an equation published in a previous work. The results showed that B increased linearly with increasing N₁. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 759–765, 2000