Isothermal Crystallization Behavior Research Articles

Effects of Addition of a Palmitic Sucrose Ester on Low-Trans-Fat Blends Crystallization in Bulk and in Oil-in-Water Emulsions

The effect of addition of a highly hydrophobic emulsifier, the palmitic sucrose ester P-170, on isothermal crystallization behavior of a high-melting fraction of milk fat (HMF) and its mixtures with 20% or 40% sunflower oil (SFO), both in bulk and in emulsion systems, were studied by nuclear magnetic resonance (NMR) and by time-resolved in situ small-angle synchrotron X-ray scattering (SAXS). NMR studies showed that the effect of P-170 on the overall isothermal crystallization kinetics in bulk phase could be either acceleration or delay. The effect was strongly dependent on supercooling. For HMF, P-170 retarded crystallization at temperatures above 29.0 ± 0.2 °C, while below that temperature, it accelerated the process. For the blends of HMF with 20% or 40% SFO, the temperature at which the behavior changed was 27.0 ± 0.2 or 26.0 ± 0.2 °C, respectively. In emulsion systems, however, the effect was always acceleration for all temperatures selected. With the aid of SAXS, it was possible to study early stage of crystallization during real time and therefore to improve our understanding of the mechanism of P-170 action. The different effects caused by P-170, as described by SFC curves, were strongly related to the effects of P-170 on fat polymorphism, specially to the value of the time interval of coexistence of the α and β′ forms. These events took place at the very beginning of crystallization and thus could not be described by the traditional X-ray techniques used in previous studies of similar systems.

Isothermal crystallization kinetics of silk fibroin fiber‐reinforced poly(ε‐caprolactone) biocomposites

AbstractBACKGROUND: Poly(ε‐caprolactone) (PCL) has attracted great attention due to its wide applications for pharmaceutical controlled released systems and implanted polymer devices. In this study, silk fibroin fiber (SF) obtained from degumming treatment of silk was used to prepare novel reinforced PCL biocomposites. The isothermal crystallization behavior of these composites was investigated using differential scanning calorimetry measurements.RESULTS: With a decrease of isothermal crystallization temperature (Tc) and an increase of fiber filler, the crystallization time of the SF/PCL composites becomes shorter, the crystallization rate constant (K) increases and the Avrami exponent (n) gradually decreases (being between 1 and 2). The crystallization of PCL and SF/PCL composites occurs in the same regime. With the gradual addition of fiber, lateral surface free energy (σ) is nearly unchanged, but fold surface free energy (σe) decreases.CONCLUSION: Heterogeneous nucleation is dominant and different growth morphologies coexist during the isothermal crystallization process of the SF/PCL hybrid systems. Although the introduction of SF obviously increases the overall crystallization rate of PCL, the growth rate constant and nucleation constant of PCL are reduced because of the confinement effect of fiber network structures on the molecular mobility of polymer molecular chains. Copyright © 2009 Society of Chemical Industry

Effect of draw ratio on the microstructure, thermal, tensile and dynamic rheological properties of insitu microfibrillar composites

Microfibrillar composites (MFCs) were prepared using different draw/stretch ratios [viz. 2, 5, 8 and 10] from polypropylene/polyethylene terephthalate (PP/PET) blends. Scanning electron microscopy [SEM] images revealed that PET microfibrils were highly oriented after melt blending and drawing. After the conversion of drawn (stretched) blends to MFCs the PET microfibrils were found to be randomly distributed in the PP matrix. The tensile strength and modulus of the MFCs were found to be higher for the samples drawn at stretch ratios 5 and 8 on account of the long PET microfibrils they possessed. The non isothermal crystallization behaviour of the neat blend (as extruded), stretched blend and the MFC was compared. The oriented PET fibrils in the stretched blend were found to have a greater nucleating effect for the crystallization of PP than the spherical PET particles in the neat blend and randomly oriented short PET fibrils in the MFC. Dynamic rheology studies indicated the storage modulus and loss modulus of MFCs were enhanced as draw ratio increases up to an optimized level beyond which they decrease. When the draw ratio increased up to the optimized level the MFCs tended to be more viscous, especially at low frequency, whereas further increasing the draw ratio resulted in a decrease in the complex viscosity. The microfibrils of PET in the MFC were found to perturb the relaxation of molten PP matrix.

Effect of unsaturated acyl chains on structural transformations in triacylglycerols

AbstractSimultaneous time‐resolved small‐angle and wide‐angle X‐ray scattering has been used in the study of the isothermal crystallization behavior, after quenching, of triacylglycerols (TAG) with 18 carbons in the hydrocarbon chains. Saturated, unsaturated TAG, their blends and mixed saturated/unsaturated TAG were studied. The mixed saturated/unsaturated TAG and their blends form an α2‐phase with a longitudinal packing different from two‐chain and three‐chain packings, which distinguishes them from the other fats. The unstable α2‐phase, observed at the initial stage of crystallization of mixed saturated/unsaturated TAG, is classified as a transient mesophase. Two dimeric units proposed for a structural model of the α2‐phase have been used to describe the structural organization of TAG molecules in the liquid state.

Isotope Effect on the Isothermal Crystallization Behavior of Isotactic Polypropylene Blends between the Deuterated and Hydrogenated Species

The effect of isotope on the isothermal crystallization behavior has been investigated for a series of isotactic polypropylene blend samples between the hydrogenated and deuterated species by using the thermal analysis technique. The analysis based on the Avrami equation revealed the crystallization rate constant k and Avrami exponent n, which were found to change systematically with the D/H content at the same degree of supercooling, reflecting the cocrystallization phenomenon of these two species. The k value was appreciably higher for the D species than for the H species. Correspondingly, the spherulite size, observed by polarized optical microscope and small-angle light scattering, was found to be larger for the blend with higher H content.

Synthesis and characterization of monomer‐casting polyamide 6/polymethacrylic ionomer blends

AbstractMonomer‐casting polyamide 6 (MCPA6)/polymethacrylic ionomer blends were synthesized by the in situ anionic ring‐opening polymerization of ϵ‐caprolactam. The polymethacrylic ionomer used in this study was a copolymer of methyl methacrylate and sodium or zinc methacrylate. Because the polymethacrylic ionomer strongly interacted with polyamide 6 (PA6) chains, it influenced the alignment of the polyamide chains. The change in the degree of the order of hydrogen bonding in MCPA6 caused by the addition of the polymethacrylic ionomer was studied with Fourier transform infrared. The change in the interaction between PA6 chains was studied with rheological measurements. The influence of the polymethacrylic ionomer on the crystallization behavior of MCPA6 was also studied with differential scanning calorimetry. The isothermal crystallization and subsequent melting behavior were investigated at the designated temperature. The commonly used Avrami equation was used to fit the primary stage of the isothermal crystallization. The Avrami exponent (n) values were evaluated to be 2 < n < 3 for the neat MCPA6 and MCPA6/polymethacrylic ionomer blends. The polymethacrylic ionomer, acting as a stumbling‐block agent in the blends, decelerated the crystallization rate with the half‐time of crystallization increasing. The polymethacrylic ionomer made the molecular chains of MCPA6 more difficult to crystallize during the isothermal crystallization process. More less perfect crystals formed in the MCPA6/polymethacrylic ionomer blends because of the interaction between the MCPA6 molecular chains and polymethacrylic ionomer. The crystallinity of the blends was depressed by the addition of the polymethacrylic ionomer. The thermal stability was also studied with thermogravimetric analysis. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Influence of pre-shearing on the crystallization of an impact-resistant polypropylene copolymer

Impact-resistant polypropylene copolymer (IPC) samples with various pre-shear histories were prepared by a Brabender Rheometer. The influence of pre-shearing on crystallization of IPC, including isothermal and nonisothermal crystallization behaviors was investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The results of nonisothermal crystallization showed that compared with as-received IPC, the temperatures referred to the peak of crystallization exotherm, Tp, were prominently elevated for pre-sheared IPC. In isothermal crystallization experiment, combining Avrami Method and Hoffman-Lauritzen Model, it was found that the half-time of crystallization (t1/2 )o f pre-sheared IPC was greatly shortened and the calculated fold surface free energy (se) within the isothermal temperatures investigated showed a large reduction. Morphological development during isothermal crystallization observed by POM clearly confirmed that the enhancement in crystallization is mainly due to the fast formation of nuclei during crystallization. Besides, using successive self-nucleation and annealing (SSA) thermal fractionation technique, changes in chain structures induced by pre- shearing were obtained. The relaxation behavior of pre-sheared IPC was also evaluated and it was found that the shear-induced enhancement in crystallization could be relaxed to various extents under annealing conditions.

A comparative study of polypropylene nucleated by individual and compounding nucleating agents. I. Melting and isothermal crystallization

AbstractIn this study, melting and isothermal crystallization behaviors of polypropylene (PP) nucleated with different nucleating agents (NAs) have been comparatively studied. α‐phase NA 1,3 : 2,4‐bis (3,4‐dimethylbenzylidene) sorbitol (DMDBS, Millad 3988), β‐phase NA aryl amides compound (TMB‐5), and their compounds were introduced into PP matrix, respectively. The crystallization and melting characteristics as well as the crystallization structures and morphologies of nucleated PP were studied by differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD), and polarized light microscopy (PLM). As indicated by previous work that a few amounts of α‐phase NA (DMDBS) or β‐phase NA (TMB‐5) has apparent nucleation effect for PP crystallization. However, the crystallization of PP nucleated with compounding NAs is dependent on the content of each NA. In the sample of PP with 0.1 wt % DMDBS and 0.1 wt % TMB‐5, the nucleation efficiency of TMB‐5 is much higher than that of DMDBS and PP crystallization is mainly nucleated by TMB‐5, and in this condition, β‐phase PP is the main crystallization structure. For the sample of PP with 0.2 wt % DMDBS and 0.2 wt % TMB‐5, 0.2 wt % DMDBS has higher nucleation efficiency than 0.2 wt % TMB5, and α‐phase is the main crystalline structure in this sample. The isothermal crystallization kinetics and crystallization structure have been analyzed in detail in this work. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Isothermal crystallization behavior of poly(L‐lactic acid)/organo‐montmorillonite nanocomposites

AbstractThe isothermal crystallization behavior of poly(L‐lactic acid)/organo‐montmorillonite nanocomposites (PLLA/OMMT) with different content of OMMT, using a kind of twice‐functionalized organoclay (TFC), prepared by melt intercalation process has been investigated by optical depolarizer. In isothermal crystallization from melt, the induction periods (ti) and half times for overall PLLA crystallization (100°C ≤ Tc ≤ 120°C) were affected by the temperature and the content of TFC in nanocomposites. The kinetic of isothermal crystallization of PLLA/TFC nanocomposites was studied by Avrami theory. Also, polarized optical photomicrographs supplied a direct way to know the role of TFC in PLLA isothermal crystallization process. Wide angle X‐ray diffraction (WAXD) patterns showed the nanostructure of PLLA/TFC material, and the PLLA crystalline integrality was changed as the presence of TFC. Adding TFC led to the decrease of equilibrium melting point of nanocomposites, indicating that the layered structure of clay restricted the full formation of crystalline structure of polymer. The specific interaction between PLLA and TFC was characterized by the Flory‐Huggins interaction parameter (B), which was determined by the equilibrium melting point depression of nanocomposites. The final values of B showed that PLLA was more compatible with TFC than normal OMMT. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers

Poly(L‐lactic acid)/silicon dioxide nanocomposite prepared via the in situ melt polycondensation of L‐lactic acid in the presence of acidic silica sol: Isothermal crystallization and melting behaviors

AbstractIn a previous article, we reported the preparation and characterization of a nanocomposite of poly(L‐lactic acid) (PLLA) and silica via the in situ melt polymerization of L‐lactic acid in the presence of acidic silica sol. In this study, the isothermal crystallization and melting behaviors of a PLLA/silicon dioxide (SiO2) nanocomposite with 5 wt % well‐dispersed SiO2 nanoparticles (PLLASN5) and pure PLLA were comparatively studied with differential scanning calorimetry and polarized optical microscopy. The SiO2 nanoparticles acted as nucleation agents in the PLLA matrix and enhanced its nucleation rate and overall crystallization rate, especially at high crystallization temperatures. However, no deleterious effect on the crystal morphology or crystallinity was observed. The crystals that formed at a low temperature were imperfect; therefore, double melting peaks occurred during the second heating scan because of melt recrystallization. With the crystallization temperature increasing, the crystals became increasingly perfect; as a result, the low melting peak increased and shifted to a higher temperature. The existence of SiO2 nanoparticles had no effect on the equilibrium temperature of the PLLA matrix. Pure PLLA and PLLASN5 have the same equilibrium temperature of 171.5°C. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Study on Crystallization Behavior of Solid-Phase Graft Copolymers of Polypropylene with Maleic Anhydride and Methyl Methacrylate

The isothermal crystallization behavior of neat polypropylene (PP) and solid-phase graft copolymers of PP with maleic anhydride and methyl methacrylate (PPMM) were compared by differential scanning calorimetry. The Avrami equation and Hoffman theory were applied to describe the isothermal crystallization kinetics. The results show that the fitted isothermal crystallization parameters are similar to the experimental data, and suggest that the Avrami equation is suitable to describe the isothermal crystallization process of PP and PPMM. The grafted side chains on PP can change the nucleation and growth of crystallization. They caused a decrease in the apparent crystallization activation energy and lateral surface free energy, and an increase in the nucleation rate. This was attributed to the grafted side chains not only acting as nucleating agent but also hindering the motion of the molecular chains and reducing the growing rate of crystallization.

Isothermal Crystallization Behaviors of Isotactic Polypropylene Nucleated with the Third Generation Sorbitol Derivative Nucleating Agents

Differential scanning calorimetry (DSC) was used to study the isothermal crystallization kinetics of isotactic polypropylene (iPP) nucleated with a third generation sorbitol derivative l,3:2,4-bis(3,4-dimethylbenzylidene) sorbitol (DMDBS). The results show that the incorporation of DMDBS can greatly shorten crystallization half time (t1/2) and increase the crystallization rate of iPP. The Avrami exponents of both virgin iPP and iPP nucleated with DMDBS are close to 3, which indicates that the addition of the nucleating agent DMDBS doesn't change the crystallization growth patterns of iPP under isothermal conditions. The Hoffman theory is adopted to calculate the σe—interfacial free energy per unit area perpendicular to PP chains of virgin iPP and iPP nucleated with DMDBS. The result shows that the addition of DMDBS can decrease the σe value of iPP so that the nucleation rate of iPP is increased greatly.

Thermal properties and crystallization behavior of ultrafine fully‐vulcanized powdered rubber particle toughened polypropylene

AbstractThermal properties and crystallization behavior of ultrafine fully‐vulcanized powdered rubber (UFPR) toughened polypropylene (PP) were studied by Differential scanning calorimetry (DSC) and Wide angle X‐ray diffraction (WAXD) measurements. It was found that the fraction of β‐form in the PP crystal increased at first, then sharply deceased up to zero with increasing UFPR content. This trend did not rely on isothermal crystallization temperature. Moreover, DSC measurements implied that UFPR particles addition affected both isothermal and nonisothermal crystallization behaviors, including the crystallization temperature and the half‐time of crystallization. Furthermore, WAXD test results indicated that the addition of UFPR induced the orientation of the crystallites more or less. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

Nonisothermal and isothermal crystallization kinetics of nylon‐12

AbstractThe isothermal and nonisothermal crystallization behavior of Nylon 12 was investigated using differential scanning calorimetry (DSC). An Avrami analysis was used to study the isothermal crystallization kinetics of Nylon 12, the Avrami exponent (n) determined and its relevance to crystal growth discussed and an activation energy for the process evaluated using an Arrhenius type expression. The Lauritzen and Hoffman analysis was used to examine the spherulitic growth process of the primary crystallization stage of Nylon 12. The surface‐free energy and work of chain folding were calculated using a procedure reported by Hoffmann and the work of chain folding per molecular fold (σ) and chain stiffness of Nylon 12 (q) was calculated and compared to values reported for Nylons 6,6 and 11. The Jeziorny modification of the Avrami analysis, Cazé and Chuah average Avrami parameter methods and Ozawa equation were used in an attempt to model the nonisothermal crystallization kinetics of Nylon 12. A combined Avrami and Ozawa treatment, described by Liu, was used to more accurately model the nonisothermal crystallization kinetics of Nylon 12. The activation energy for nonisothermal crystallization processes was determined using the Kissinger method for Nylon 12 and compared with values reported previously for Nylon 6,6 and Nylon 11. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

Effects of silver nanoparticles on the dynamic crystallization and physical properties of syndiotactic polypropylene

AbstractThe effects of silver (Ag) nanoparticles on the physical properties of syndiotactic PP (sPP) were investigated concentrating on the isothermal melt crystallization behavior under shear. sPP with 5 wt % Ag nanoparticles presented higher crystallization temperature (Tc) and heat of crystallization (ΔHc) than pure sPP. At 90°C, the Ag nanoparticles had little effect on the induction time of crystallization but a little increased the half‐time (t1/2) for the crystallization. At 100°C, however, the induction time was decreased with increasing the Ag content and the t1/2 was decreased up to the Ag content of 0.5 wt %. DSC melting endotherms exhibited double melting peaks when crystallized at 90°C under shear but a single melting peak when crystallized at 100°C. The WAXD patterns exhibited that the presence of Ag nanoparticles did not produce any change in the crystal structure of sPP. The tensile strength of sPP is little changed up to the Ag content of 0.1 wt % but it was decreased with further addition. In addition, the introduction of less than 0.1 wt % Ag increased the elongation at break, but further addition decreased it abruptly. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

Miscibility and isothermal crystallization behavior of polyamide 6/poly(vinyl alcohol) blend

AbstractAn investigation of miscibility and isothermal crystallization behavior of Polyamide 6 (PA6)/Poly(vinyl alcohol) (PVA) blends was conducted. Fourier transform infrared spectra (FTIR) analysis indicated that the interactions between the carbonyl groups of PA6 and hydroxyl groups of PVA increase as the weight ratios of PA6 to PVA of PA6/PVA specimens increase. This interaction between PA6 and PVA leads to their miscibility in the amorphous region and even some extent effects on their crystal phase, respectively. Further isothermal crystallization behavior of PA6/PVA indicate that the miscibility of PVA in PA6 leading difficulty in crystallization of PA6. Several kinetics equations are employed to describe the effects of PVA on the crystallization properties of PA6 in PA6/PVA blends in detail. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1360–1368, 2008

Effect of graft modification with poly(N‐vinylpyrrolidone) on thermal and mechanical properties of poly (3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)

AbstractPoly(N‐vinylpyrrolidone) (PVP) groups were grafted onto poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) backbone to modify the properties of PHBV and synthesize a new novel biocompatible graft copolymer. The effect of graft modification with PVP on the thermal and mechanical properties of PHBV was investigated. The thermal stability of grafted PHBV was remarkably improved while the melting temperature (Tm) was almost not affected by graft modification. The isothermal crystallization behavior of samples was observed by polarized optical microscopy and the results showed that the spherulitic radial growth rates (G) of grafted PHBV at the same crystallization temperature (Tc) decreased with increasing graft yield (graft%) of samples. Analysis of isothermal crystallization kinetics showed that both the surface free energy (σe) and the work of chain‐folding per molecular fold (q) of grafted PHBV increased with increasing graft%, implying that the chains of grafted PHBV are less flexible than ungrafted PHBV. This conclusion was in agreement with the mechanical testing results. The Young's modulus of grafted PHBV increased while the elongation decreased with increasing graft%. The hydrophilicity of polymer films was also investigated by the water contact angle measurement and the results revealed that the hydrophilicity of grafted PHBV was enhanced. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

Comparison Between Isothermal Cold and Melt Crystallization of Polylactide/Clay Nanocomposites

The isothermal cold and melt crystallization behavior of intercalated polylactide (PLA)/clay nanocomposites (PLACNs) were studied using differential scanning calorimetry (DSC), polarized optical microscope (POM), X-ray diffractometer (XRD) and Fourier Transform Infra-Red Spectrometer (FT-IR). The results show that the degree of crystallinity of PLA matrix decreases monotonously with increasing clay loadings for both the cold and melt crystallization. The cold crystallized sample shows a double melting behavior and lower melting temperature compared to that of melt-crystallized sample, especially in the presence of clay. The crystallization kinetics was then analyzed by the Avrami and Lauritzen-Hoffman methods for further comparison between these two crystallization behaviors. The results reveal that PLA and its nanocomposites present higher activation energy in melt crystallization than that in cold crystallization due to the reptation of entire polymer chains. The addition of clay facilitates the overall kinetics of melt crystallization, which is attributed to both the nucleation effect of clay and enhanced diffusion of PLA chains. However, for cold crystallization, only very small amounts of clay can slightly increase the kinetics, while larger amounts impede the process. The presence of clay leads to a diffusion-controlled growth of nucleation of PLA matrix in the cold crystallization process and, the hindrance effect of clay hence becomes the dominant factor gradually with increasing clay loadings in the case of high-rate nucleation.

Comparison Between Isothermal Cold and Melt Crystallization of Polylactide/Clay Nanocomposites

The thermoluminescence (TL) of undoped and Dy3+ doped ZrO2 nanocrystals under beta-ray irradiation is reported. The TL glow curves are the result of the overlapping of four TL peaks produced partly by the intrinsic defect of highly asymmetrical monoclinic structure and partly due to defects produced during the synthesis process. The introduction of dopant ions induces changes in the glow curve due to the enhancement of high temperature peaks intensity. The results show that both undoped and doped ZrO2 nanocrystalline phosphor present good TL efficiency as well as good dose response which qualify them as a potential beta-ray dosimeter.

Isothermal crystallization and mechanical behavior of ionomer treated sisal/HDPE composites

Isothermal crystallization behavior and mechanical properties of ionomer-treated sisal fibres reinforced high-density polyethylene (HDPE) composites have been investigated. Avrami analysis of the crystallization kinetics showed high crystallization rate ( K n ) and short crystallization half time ( t 0.5) for composites compared to neat HDPE, indicating strong nucleating ability of sisal fibres. The crystallization activation energy ( E a) of the composites decreased with increasing fibre content. The polarizing optical microscopy showed the occurrence of transcrystallization at the fibre–matrix interface. The HDPE/sisal composites displayed superior tensile and flexural properties compared to neat HDPE. For these composites, predictions of Young's modulus using the Modified Rule of Mixtures and Cox model correlated well with the experimental data.