Fold Surface Free Energy Research Articles

Melt crystallized polyamide 6.6 and its copolymers, Part I. Melting point – Lamellar thickness relations in the homopolymer

The effect of isothermal crystallization temperature and time on the lamellar thickness and the melting behavior of polyamide 66 has been studied. Measurements were made of the melting temperature, crystallinity, and the long period. When calculated in the conventional direct manner, for samples crystallized isothermally, the calculated lamellar thickness was found to vary only from 2.4 to 3.2 nm over the entire range of conditions considered. When viewed in a non-critical fashion the polymer appears to conform to normal behavior including typical T c vs. T m behavior on a Hoffman–Weeks plot and apparent linearity in a Gibbs–Thompson plot. SAXS data indicates that there are only small changes in the lamellar thickness occurring over the entire crystallization range despite major changes in the melting point. Accordingly the Gibbs–Thompson plot shows major amounts of scatter, which are well beyond the experimental errors involved. The changes in melting temperature appear to be a result of changes in the structure of the fold surface on the basis of the conventional lamellar thickness analysis. In particular they appear to be due to changes in the character of the surface related to the hydrogen bonding and to the relative amounts of acid and amine segments present in the folds. When a more thorough analysis of the SAXS data are conducted, using a one dimensional correlation function approach, calculation of the crystal core thicknesses and “interfacial layer” thicknesses, a different picture emerges. In this case, the total lamellar thickness remains approximately constant at 2 repeat units in length with isothermal crystallization temperature, however, the core thickness increases with increasing crystallization temperature and time, from 1.5 to 2 repeat units in length, whereas the “interfacial layer” thickness is substantial at lower temperatures and times. When the core thickness is used in a Gibbs–Thompson plot the equilibrium melting temperature is found to be 303.7 °C (cf. 301 °C from solution grown crystals). However, the fold surface free energy is found to be 23.7 erg/cm 2 much lower than the value of 74.6 erg/cm 2 characteristic of solution grown crystals. Such a large discrepancy is believed to be a result of the highly polar solvents used in solution based studies generating the widely accepted “acid folds”. The difference may be because of a switch to folds containing six methylene groups from the diamine mer in the bulk case. Since the polymer is known to crystallize in the hexagonal state and reorganize during cooling to the regularly reported structure it is possible that the “interfacial thickness” is indeed a disordered surface layer within the crystalline lamella that originates from the precursor hexagonal phase during its formation, rather than the conventional disordered surface interpretation, applicable to polymers such as polyethylene. It is also possible that it is reflective of disorder induced in surface layers within the crystal due to the conformational changes occurring during this crystal–crystal transition. For these reasons, we prefer to refer to the “interfacial layer” obtained from SAXS calculations as an innerlayer.

Isothermal cold crystallization kinetics of polylactide/nucleating agents

AbstractThe isothermal cold crystallization kinetics of polylactide (PLA)/nucleating agents (CaCO3, TiO2, and BaSO4, content from 0.5–2.0 wt %) was investigated by differential scanning calorimetry in the temperature range of 120–124°C. With blending nucleating agents, the crystallinity of PLA had a maximum crystallinity of 14.9%. Crystallization rate decreased with increasing crystallization temperature in the researched content range. The crystallization rate followed the Avrami equation with the exponent n around 4.5. From Lauritzen–Hoffman equation, the nucleation parameter Kg was estimated. And from the value of Kg, regime II crystallization behavior can be concluded. Then the lateral and fold surface free energy were calculated from Kg. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 310–317, 2007

Effect of nucleating agents on crystallization kinetics of PET

Effects of three nucleating agents concluding talc, sodium benzoate (SB) and an ionomer (Ion., Na+) on crystal- lization of poly(ethylene terephthalate) (PET) were studied by differential scanning calorimetry (DSC) and polarized opti- cal microscope (POM), the parameters of crystallization kinetics were obtained through Avrami and Ozawa equations. The fold surface free energy σe of pure PET and PET/nucleating agent blends was calculated by Hoffman-Lauritzen theory. The results indicate that the three kinds of nucleating agents increase the crystallization rate constant through promoting their nucleating effect for PET crystallization, among which SB is the best one with the same content. The crystallization mode of PET might shift from three-dimensional growth to two-dimensional growth by the addition of the nucleating agents. The values of σe of PET/nucleating agent blends are much less than that of pure PET, and PET/SB (99:1) blend has the least value of σe (18.2 mJ/m2). The conclusion based on Hoffman theory is similar to the analysis by Avrami and Ozawa equa- tions.

Structure and Morphology of Poly(ε-caprolactone)/Chlorinated Polyethylene (PCL/PECl) Blends Investigated by DSC, Simultaneous SAXS/WAXD, and Elemental Mapping by ESI-TEM

In this work, the structure and morphology of miscible blends of poly(ε-caprolactone) and chlorinated polyethylene with 48% chlorine weight content (PCL/PECl) were studied by differential scanning calorimetry (DSC), simultaneous small and wide-angle X-ray scattering (SAXS/WAXD), and electron spectroscopy imaging in the transmission electron microscope (ESI-TEM). A unique glass transition temperature was obtained in each blend. In addition to this, the heat capacity and the width of the glass transition did not have a linear behavior with blend compositions. These facts correlate with the presence of microheterogeneities originated from different local compositions and densities of interactions in each blend. A consistent picture of the mode of segregation of PECl in the blend was obtained. For higher concentration of PCL, the volume fraction of lamellar stacks in the samples decreased as a function of the PECl content, indicating preferential interfibrillar localization of the amorphous component. For lower PCL concentration, interespherulitic segregation was the dominant mode. Elemental maps of chlorine confirmed these results and also revealed changes in the concentration of this element depending on its localization in the microstructure of the system. Gradients of chlorine concentration were measured in larger amorphous regions of the 40/60 and 20/80 PCL/PECl blends. Calculations of the one-dimensional correlation function probed the reduction of the lamellar thickness of PCL when the quantity of PECl in the blend was increased. Such a tendency could be rationalized if the reduction of the fold surface free energy was a dominant factor in terms of the reduction of the degree of supercooling in the final crystal thickness.

Crystallization Kinetics of Linear and Long‐Chain Branched Polypropylene

Isothermal crystallization kinetics of linear polypropylene (PP) and long‐chain branched (LCB) PPs were investigated on the basis of the Avrami theory. The Avrami exponents of LCB PPs are smaller than that of linear PP; moreover, they decrease with an increasing LCB level. The crystallization half‐time of LCB PP depends more strongly on the crystallization temperature than does that of linear PP. The Lauritzen‐Hoffman theory was used to study the effect of LCB on the crystal growth rate of PP. The fold surface free energy of LCB PP is lower than that of linear PP; moreover, it decreases with an increasing LCB level. However, when the LCB level is over a certain value, the fold surface free energy increases again. Furthermore, the crystal structures of linear PP and LCB PPs were studied by wide‐angle X‐ray diffraction (WAXD); it was observed that linear PP can crystallize in the α and β forms, while LCB PPs have only the α crystalline form. Moreover, the relative intensities of different α peaks were also influenced by the LCB level.

Star-shaped poly(ɛ-caprolactone) with polyhedral oligomeric silsesquioxane core

A readily available octa(3-chloropropyl) polyhedral oligomeric silsesquioxane (POSS) [(ClCH 2CH 2CH 2) 8Si 8O 12] framework was used to prepare octa(3-hydroxypropyl) POSS [(HOCH 2CH 2CH 2) 8Si 8O 12], which was further used as an initiator to synthesize star poly(ɛ-caprolactone) with POSS core via ring-opening polymerization catalyzed by Stannous (II) octanoate [Sn(Oct) 2]. The organic–inorganic star PCLs were characterized by means of gel permeation chromatograph (GPC), Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (NMR). The wide-angle X-ray diffraction (WAXRD) experiments indicate that the presence of POSS cores did not alter the crystal structure of PCL. The star PCLs exhibited enhanced melting temperatures in comparison with the linear counterpart. The isothermal crystallization kinetics shows that both the overall crystallization rate and the spherulitic growth rate of the star PCLs increased with increasing the concentration of POSS (or with decreasing the arm lengths of the stars). The fold surface free energy of the star PCLs decreased with increasing the concentration of POSS. These results could be interpreted based on the effect of the heterogeneous nucleation of POSS cores, which accelerates the process of crystallization.

Isothermal crystallization kinetics of poly(butylene terephthalate)/attapulgite nanocomposites

AbstractPoly(butylene terephthalate) (PBT)/organo‐attapulgite (ATT) nanocomposites containing 2.5 and 5 wt % nanoparticles loadings were fabricated via a simple melt‐compounding approach. The crystal structure and isothermal crystallization behaviors of PBT composites were studied by wide‐angle X‐ray diffraction and differential scanning calorimetry, respectively. The X‐ray diffraction results indicated that the addition of ATT did not alter the crystal structure of PBT and the crystallites in all the samples were triclinic α‐crystals. During the isothermal crystallization, the PBT nanocomposites exhibited higher crystallization rates than the neat PBT and the varied Avrami exponents when compared with the neat PBT. At the same time, the regime II/III transition was also observed in all the samples on the basis of Hoffman‐Laurizten theory, but the transition temperature increased with increasing ATT loadings. The fold surface free energy (σe) of polymer chains in the nanocomposites was lower than that in the neat PBT. It should be reasonable to treat ATT as a good nucleating agent for the crystallization of PBT, which plays a determinant effect on the reduction in σe during the isothermal crystallization of the nanocomposites, even if the existence of ATT could restrict the segmental motion of PBT. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2112–2121, 2006

Crystallization and melting behavior of silica nanoparticles and poly(ethylene 2,6-naphthalate) hybrid nanocomposites

Organic and inorganic hybrid nanocomposites based on poly(ethylene 2,6-naphthalate) (PEN) and silica nanoparticles were prepared by a melt blending process. In particular, polymer nanocomposites consisting mostly of cheap conventional polyesters with very small quantities of inorganic nanoparticles are of great interest from an industrial perspective. The crystallization behavior of PEN/silica hybrid nanocomposites depended significantly on silica content and crystallization temperature. The activation energy of crystallization for PEN/silica hybrid nanocomposites was decreased by incorporating a small quantity of silica nanoparticles. Double melting behavior was observed in PEN/silica hybrid nanocomposites, and the equilibrium melting temperature decreased with increasing silica content. The fold surface free energy of PEN/silica hybrid nanocomposites decreased with increasing silica content. The work of chain folding (q) for PEN was estimated as 7.28×10−20 J per molecular chain fold, while theq values for the PEN/silica 0.9 hybrid nanocomposite was 3.71×10−20 J, implying that the incorporation of silica nanoparticles lowers the work required to fold the polymer chains.

Miscibility and crystallization behavior of PBT/epoxy blends

AbstractThe miscibility and the isothermal crystallization kinetics for PBT/Epoxy blends have been studied by using differential scanning calorimetry, and several kinetic analyses have been used to describe the crystallization process. The Avrami exponents n were obtained for PBT/Epoxy blends. An addition of small amount of epoxy resin (3%) leads to an increase in the number of effective nuclei, thus resulting in an increase in crystallization rate and a stronger trend of instantaneous three‐dimensional growth. For isothermal crystallization, crystallization parameter analysis showed that epoxy particles could act as effective nucleating agents, accelerating the crystallization of PBT component in the PBT/Epoxy blends. The Lauritzen–Hoffman equation for DSC isothermal crystallization data revealed that PBT/Epoxy 97/3 had lower nucleation constant Kg than 100/0, 93/7, and 90/10 PBT/Epoxy blends. Analysis of the crystallization data of PBT/Epoxy blends showed that crystallization occurs in regime II. The fold surface free energy, σe = 101.7–58.0 × 10−3 J/m2, and work of chain folding, q = 5.79–3.30 kcal/mol, were determined. The equilibrium melting point depressions of PBT/Epoxy blends were observed and the Flory–Huggins interaction parameters were obtained. It indicated that these blends were thermodynamically miscible in the melt. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1320–1330, 2006

Crystallization behaviour of cellulose acetate butylate/poly(butylene succinate)‐co‐(butylene carbonate) blends

AbstractThe kinetics of the isothermal crystallization process from the melt of pure poly(butylene succinate)‐co‐(butylene carbonate) (PBS‐co‐BC) and its blends with cellulose acetate butylate (CAB) (10–30 wt%) was studied by differential scanning calorimetry (DSC) and the well‐known Avrami equation. In the blends, the overall crystallization rate of PBS‐co‐BC became slower with increasing CAB content. The equilibrium melting temperature ($T_{\rm {m}}^{\rm {eq}}$) of PBS‐co‐BC decreased with increasing CAB content, which was similar to that with other miscible crystalline/amorphous polymer blends. The slower crystallization kinetics of PBS‐co‐BC in the blends was explicable in terms of a diluent effect of the CAB component. By application of Turnbull–Fisher kinetic theory for polymer–diluent blend systems, the surface free energy (σe) of pure PBS‐co‐BC and of the blends was obtained, indicating that the blend with CAB resulted in a decrease in the surface free energy of folding of PBS‐co‐BC lamellar crystals. Copyright © 2006 Society of Chemical Industry

Shear‐Enhanced Nucleation of Isotactic Polypropylene in Limited Space

The nucleation rate was measured by directly counting the number of nuclei, which were developed while an isotactic polypropylene melt was flowing under shear in a thin film. The nucleation rate was enhanced with an increased rate of shear, e.g., by a factor of 10 larger at the rate of shear of 14 s−1 compared with the quiescent state, at 134°C. The ratio of the shear‐enhanced nucleation rate to the nucleation rate in the quiescent state was larger at a higher temperature of crystallization, i.e., about 10 times at 134°C to 590 times at 140°C. The increase of the nucleation rate under shear flow was explained by a reduction of the lateral and end (fold) surface free energies; the product σ s 2 σ e decreased to 3.2×10−7 for the sheared melt, from 6.0×10−7 (J m−2)3 for the isotropic state. The free energy reduction was caused by transition of the nucleus formation mode from three‐dimensional folded chain nuclei to two‐dimensional bundle nuclei, in which chains lie down on the glass substrate, aligning parallel to the flow direction.

Effect of the structure on the morphology and spherulitic growth kinetics of polyolefin in‐reactor alloys

AbstractFour polyolefin in‐reactor alloys with different compositions and structures were prepared by sequential polymerization. All the alloys were fractionated into five fractions: a random copolymer of ethylene and propylene (25°C fraction), an ethylene–propylene segmented copolymer (90°C fraction), an ethylene homopolymer (110°C fraction), an ethylene–propylene block copolymer (120°C fraction), and a propylene homopolymer plus a minor ethylene homopolymer of high molecular weight (>120°C fraction). The effect of the structure on the morphology and spherulitic growth kinetics of the polypropylene (PP) component in the alloys was investigated. The polyolefin alloys containing a suitable block copolymer fraction and a larger amount of PP had a more homogeneous morphology, and the crystalline particles were smaller. Quenching the polyolefin alloys led to smaller crystallites and a more homogeneous morphology as well. Isothermal crystallization was carried out above the melting temperature of polyethylene, and the growth of PP spherulites was monitored with polarized optical microscopy with a hot stage. The alloys with higher propylene contents exhibited a faster spherulitic growth rate. The fold surface free energy was derived, and it was found that a large amount of block copolymer fractions and random copolymer fractions could reduce the fold surface free energy. The structure of the alloys also affected the crystallization regime of PP. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 632–638, 2005

Single crystal morphology of star-branched polyesters with crystallisable poly( ε-caprolactone) arms

Star-branched polymers consisting of poly( ε-caprolactone) (PCL) attached to third generation dendrimer, hyperbranched and dendron cores have been studied together with linear PCL analogues. The degree of polymerisation of the PCL arms of the star-branched polymers ranged from 14 to 81. Single crystals were grown from dilute solution and studied by transmission electron microscopy. Single crystals of linear PCL were multilayer hexagons with flat or slightly curved {110} and {100} faces. These single crystals were larger along [010] than along [100]. Single crystals of star-branched PCL showed the same basic shape, but with many crystallographic and irregular steps on the lateral crystal faces. The width of the micro-faces was typically 100–300 nm. These single crystals were more extended along [100] than along [010]. It is proposed that the high fold surface free energy and the constrained character of the star-branched polymers favour the formation of steps on the growth faces. Globular polycrystalline aggregates were also observed. They originated from a more concentrated polymer phase following phase separation of the solution. In the case of the star-branched polymers, lamellar branching was observed with a 30° angle between the crystals arms.

Isothermal crystallization kinetics of PP in PP/Mg(OH)2 composites

AbstractThe crystallization and melting behavior of PP/Mg(OH)2 composites was investigated, and the crystallization kinetic parameters and thermal characteristics were investigated according to the Avrami method. Optical polarizing microscope (POM) analysis suggested that the presence of Mg(OH)2 particles gave rise to an increase in the number of nuclei and a decrease in PP spherulitic size. The Avrami exponent n of the PP and composites increased with increasing crystallization temperature, and markedly deceased with the addition of low Mg(OH)2 content. A significant increase in crystallization kinetic constant, and a decrease in crystallization half time of PP were observed in the presence of Mg(OH)2 particles, indicating a heterogeneous nucleating effect of Mg(OH)2 upon crystallization of PP. The melting temperature and equilibrium melting temperature of PP in the composites decreased with increasing the Mg(OH)2 content, which is directly related to the size of the PP crystals. The difference of PP melting enthalpies in the PP and composites demonstrated that the presence of Mg(OH)2 can effectively enhance the crystalline of PP. The crystallization thermodynamics of PP and composites were studied according to the Hoffman theory. Surface free energy of PP chain folding for crystallization of PP/Mg(OH)2 composites was lower than that of PP, confirming the heterogeneous nucleation effect of Mg(OH)2. However, the evaluation of the nucleation activation energy of PP suggested the presence of a large amount of Mg(OH)2 particles in the PP matrix reduced the mobility of PP segments and restricted the development of PP nucleation. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1914–1923, 2005

Lamellar morphologies and crystal stability of syndiotactic polystyrene in α-crystalline form

Syndiotactic polystyrene (sPS) samples melt-crystallized into neat α″ hexagonal modifications were prepared at various temperatures thoroughly for the extensive morphological studies. Lamellar morphologies of the as-prepared sPS samples were investigated using small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). Absence of a discernible scattering peak was found for SAXS conducted at room temperature, resulting from a negligible difference in the electron density between the lamellar and amorphous layers. To enhance the scattering contrast and strength, SAXS was carried out at 180 °C to obtain more reliable morphological parameters. Due to the broad thickness distribution of morphological features as revealed from the TEM observations, a pronounced variation is found for the long periods derived from the Bragg's law, one-dimensional correlation function, and interface distribution function of the SAXS data. In addition, relatively irregular packing of lamellar stacks with short lateral dimensions was detected in the as-prepared α″-form sPS, leading to the absence of spherulitic birefringence under polarized optical microscopy. Based on the interface distribution function analysis of the SAXS intensity profiles, the lamellar thicknesses were estimated. Using the Gibbs–Thomson relation, the ratio of fold surface free energy ( σ e) to the fusion enthalpy ( Δ H f 0 ) for α″-form sPS was successfully deduced to be ca. 0.057 nm, which is lower than that of β′-form sPS, ca. 0.12 nm. On this basis, a comparison of critical lamellar thicknesses for α″- and β′-form sPS at various crystallization temperatures is provided and the crystal stability associated with the lamellar thickness is discussed as well.

Miscibility, Specific Interactions, and Spherulite Growth Rates of Binary Poly(acetoxystyrene)/Poly(ethylene oxide) Blends

The binary poly(acetoxystyrene)/poly(ethylene oxide) (PAS/PEO) blend system is fully miscible, as evidenced by a single glass transition temperature over a full range of compositions when analyzed by differential scanning calorimetry analysis, as a result of weak C−H···O hydrogen-bonding interactions between the carbonyl groups of PAS and the methylene groups of PEO. One- and two-dimensional correlation spectroscopies provide positive evidence for this specific interaction between the two polymers. In addition, a negative polymer−polymer interaction parameter “χ12” was calculated using the Flory−Huggins equation based on the melting depression of PEO. The presence of an amorphous PAS phase results in a reduction in the spherulite growth rate of PEO. Both the values of nucleation constant and the surface free energy of chain folding of PEO decrease with increasing PAS content, which indicates that the crystallization ability of PEO increases correspondingly.

Development of lamellar morphology in poly(ethylene terephthalate)/polycarbonate blends

We have studied the lamellar-level morphology of poly(ethylene terephthalate) (PET)/polycarbonate (PC) blends using small-angle X-ray scattering (SAXS). Measurements were made as a function of the holding time in the melt. We determined the morphological parameters at the lamellar level by correlation function analysis of the SAXS data. An increased amorphous layer thickness was identified in the blend, indicating that some PC was incorporated into the interlamellar regions of PET during crystallization. The blend also exhibits a larger lamellar crystalline thickness (l c ) than that of pure PET. A possible reason for the increase inl c is that the inclusion of the PC molecules in the interlamellar regions causes an increase in the surface free energy of folding. At the early stage of isothermal crystallization, we observed a rapid drop in the value ofl c in the blend; this finding indicates that a relatively large fraction of secondary crystals form during the primary crystallization. In contrast, the value ofl c for the sample that underwent a prolonged holding time increased with time in the secondary crystallization-dominant regime; this observation suggests that the disruption of chain periodicity, which results from transesterification between the two polymers, favors the development of fringed micellar crystals that have larger values ofl c , rather than the development of normal chain-folded crystals.

The effect of end groups of PEG on the crystallization behaviors of binary crystalline polymer blends PEG/PLLA

The effect of end groups (2OH, 1OH, 1CH 3 and 2CH 3) of poly(ethylene glycol) (PEG) on the miscibility and crystallization behaviors of binary crystalline blends of PEG/poly( l-lactic acid) (PLLA) were investigated by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). A single glass-transition temperature was observed in the DSC scanning trace of the blend with a weight ratio of 10/90. Besides, the equilibrium melting point of PLLA decreased with the increasing PEG. A negative Flory interaction parameter, χ 12, indicated that the PEG/PLLA blends were thermodynamically miscible. The spherulitic growth rate and isothermal crystallization rate of PEG or PLLA were influenced when the other component was added. This could cause by the change of glass transition temperature, T g and equilibrium melting point, T 0 m. The end groups of PEG influenced the miscibility and crystallization behaviors of PEG/PLLA blends. PLLA blended with PEG whose two end groups were CH 3 exhibited the greatest melting point depression, the most negative Flory interaction parameter, the least fold surface free energy, the lowest isothermal crystallization rate and spherulitic growth rate, which meant better miscibility. On the other hand, PLLA blended with PEG whose two end groups were OH exhibited the least melting point depression, the least negative Flory interaction parameter, the greatest fold surface free energy, the greatest isothermal crystallization rate and spherulitic growth rate.

Effect of poly(propylene carbonate) on the crystallization and melting behavior of poly(β‐hydroxybutyrate‐co‐β‐hydroxyvalerate)

AbstractThe crystallization and melting behavior of poly(β‐hydroxybutyrate‐co‐β‐hydroxyvalerate) (PHBV) and a 30/70 (w/w) PHBV/poly(propylene carbonate) (PPC) blend was investigated with differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR). The transesterification reaction between PHBV and PPC was detected in the melt‐blending process. The interaction between the two macromolecules was confirmed by means of FTIR analysis. During the crystallization process from the melt, the crystallization temperature of the PHBV/PPC blend decreased about 8°C, the melting temperature was depressed by 4°C, and the degree of crystallinity of PHBV in the blend decreased about 9.4%; this was calculated through a comparison of the DSC heating traces for the blend and pure PHBV. These results indicated that imperfect crystals of PHBV formed, crystallization was inhibited, and the crystallization ability of PHBV was weakened in the blend. The equilibrium melting temperatures of PHBV and the 30/70 PHBV/PPC blend isothermally crystallized were 187.1 and 179°C, respectively. The isothermal crystallization kinetics were also studied. The fold surface free energy of the developing crystals of PHBV isothermally crystallized from the melt decreased; however, a depression in the relative degree of crystallization, a reduction of the linear growth rate of the spherulites, and decreases in the equilibrium melting temperature and crystallization capability of PHBV were detected with the addition of PPC. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2514–2521, 2004

Morphology and spherulitic growth kinetics in poly(ethylene oxide)/poly(n‐butyl methacrylate) blends

AbstractResults of a study concerning the morphology and the spherulite growth rates of poly(ethylene oxide) (PEO) in binary blends with poly(n‐butyl methacrylate) (PnBMA) are reported. Microscopic observations show that blending causes the spherulite structure to become coarser and less birefringent and confirms that the spherulitic growth rates of PEO were reduced by the addition of PnBMA. X‐ray diffraction studies show no change in the unit cell dimensions and a decrease in the degree of crystallinity upon blending. Analysis of the spherulite radial growth rate data by using Lauritzen–Hoffman theory indicates that crystallization in the range of 300 to 330 K occurs solely within regime III. The calculated surface free energy of folding, σe, for pure PEO is 57 erg cm−2 and decreases with increasing the content of PnBMA in the blend. Copyright © 2004 Society of Chemical Industry