Physical properties, crystallization kinetics, and spherulitic growth of well-defined poly(ε-caprolactone)s with different arms

Both well defined star-shaped poly(ε-caprolactone) having four arms (4sPCL) and six arms (6sPCL) and linear PCL having one arm (LPCL) and two arms (2LPCL) were synthesized and then used for the investigation of physical properties, isothermal and nonisothermal crystallization kinetics, and spherulitic growth. The maximal melting point, the cold crystallization temperature, and the degree of crystallinity of these PCL polymers decrease with the increasing number of polymer arms, and they have similar crystalline structure. The isothermal crystallization rate constant (K) of these PCL polymers is in the order of K_2LPCL>K_LPCL>K_4sPCL>K_6sPCL. Notably, the K of linear PCL decreases with the increasing molecular weight of polymer while that of star-shaped PCL inversely increases. The variation trend of K over the number of polymer arms or the molecular weight of polymer is consistent with the analyses of both nonisothermal crystallization kinetics and the spherulitic growth rate. These results indicate that both the number of polymer arms and the molecular weight of polymer mainly controlled the isothermal and nonisothermal crystallization rate constants, the spherulitic growth rate, and the spherulitic morphology of these PCL polymers.     

Effect of morphology on the crack propagation of the semicrystalline polyester poly(1,4-dimethylene-trans-cyclohexyl suberate)

Crack propagation of the semicrystalline polymer poly(1,4-dimethylene-trans-cyclohexyl suberate) (MCS) was studied as a function of polymer morphology. MCS was characterized in terms of degree of crystallinity and crystal growth kinetics. Spherulitic band size and radius show similar temperature dependencies. The energy to propagate a crack was correlated with spheruliticr adius for a low-molecular-weight material (M_n = 24 500). Brittle fracture occurs in this material with little large-scale plastic deformation. What plastic deformation there is, however, correlated with spherulitic band orientation. A higher-molecular-weight sample (M_n = 38 000) shows plastic deformation over the entire temperature range studied. Energy to fracture agrees with a modified Griffith criterion in which the characteristic dimension is spherulitic radius. Annealing experiments show that energy to fracture is controlled by lamellar thickness, decreasing with increasing thickness. Fracture morphology shows little interspherulitic failure, with intraspherulitic failure (low-molecular-weight material) or plastic deformation (high-molecular-weight material) being the prevalent modes.     

Crystallization kinetics and morphology of polymer blends of poly(tetramethyl-p-silphenylene siloxane) fractions

The crystallization behaviour of polymer blends or mixtures of the same system has been studied over a wide range of molecular weight and crystallization temperatures. Blends were made by mixing fractionated polymer samples. The spherulitic growth in these mixtures is dependent upon the number-average molecular weight of the system at the shorter chain lengths, but then becomes insensitive to molecular weight values when about 10⁵ to 10⁶ are reached. The growth rate kinetics of mixtures can be described by a kinetic model used for fractionated poly(tetramethyl-p-silphenylene siloxane) (TMPS) polymers. The crystal surface energies deduced from these rate data are molecular weight dependent as are the pre-exponential and transport factors in the rate equation. These parameters are explained in terms of the crystallite morphology. Mixtures (as well as fractions themselves) of all polymer fractions ranging from the monomer to the highest molecular weight (10⁶ approximately) have similar morphological features and form negatively birefringent spherulites. Although molecular weight segregation appears to play an important role in crystallization at comparatively small undercoolings, its influence seems to be minimal at large undercoolings (close to or below the growth rate maxima). Very low molecular weight additives significantly affect the overall crystallization kinetics. Compared to the undiluted sample, mixtures so formed have lower observed melting points and glass transition temperatures. Rates of crystallization are generally facilitated by the diluent with the peak in the growth rate being displaced to lower temperatures. The growth rates for diluted over the undiluted polymer at similar undercoolings are usually larger. At high molecular weights the log of the spherulitic growth rate varies as $\text{M}{}^{\mathrm{<mtext>?1</mtext><mtext>2</mtext>}}{}_{\mathrm{n}}$, over a considerable range, but at low molecular weight values the rate depends more strongly on M_n approaching a limit of M^?1.2_n as the monomeric state is approached.     

Behaviour of the miscibility of poly(ethylene oxide)/liquid crystal blends

The microscopic behaviour of blends of poly(ethylene oxide) with two different low molecular weight liquid crystals (LC) was studied in order to evaluate miscibility. One of the liquid crystal components had a phase transition temperature lower than the melting temperature of poly(ethylene oxide) (PEO), and the other a higher value. The low molecular weight liquid crystal components were 4-cyano-4′-n-heptylbiphenyl (7CB) and p-cyanophenyl p-pentyloxybenzoate (pCP). Thermal analysis and polarized optical and scanning electron microscopy were employed. The melting temperature (T_m) depression of PEO increased with LC content in the blend, suggesting that the PEO was miscible with both liquid crystals in the isotropic phase. The spherulitic structural morphology of the semicrystalline components is affected by the presence of liquid crystals. © 1998 SCI.     

Crystallization kinetics and morphology of poly(butylene succinate)/poly(vinyl phenol) blend

Biodegradable crystalline poly(butylene succinate) (PBSU) can form miscible polymer blends with amorphous poly(vinyl phenol) (PVPh). The isothermal crystallization kinetics and morphology of neat and blended PBSU with PVPh were studied by differential scanning calorimetry (DSC), optical microscopy (OM), wide angle X-ray diffraction (WAXD), and small angle X-ray scattering (SAXS) in this work. The overall isothermal crystallization kinetics of neat and blended PBSU was studied with DSC in the crystallization temperature range of 80-88 °C and analyzed by applying the Avrami equation. It was found that blending with PVPh did not change the crystallization mechanism of PBSU, but reduced the crystallization rate compared with that of neat PBSU at the same crystallization temperature. The crystallization rate decreased with increasing crystallization temperature, while the crystallization mechanism did not change for both neat and blended PBSU irrespective of the crystallization temperature. The spherulitic morphology and growth were observed with hot stage OM in a wide crystallization temperature range of 75-100 °C. The spherulitic morphology of PBSU was influenced apparently by the crystallization temperature and the addition of PVPh. The linear spherulitic growth rate was measured and analyzed by the secondary nucleation theory. Through the Lauritzen-Hoffman equation, some parameters of neat and blended PBSU were derived and compared with each other including the nucleation parameter (K_g), the lateral surface free energy (σ), the end-surface free energy (σ_e), and the work of chain folding (q). Blending with PVPh decreased all the aforementioned parameters compared with those of neat PBSU; however, the decrease extent was limited. WAXD result showed that the crystal structure of PBSU was not modified after blending with PVPh. SAXS result showed that the long period of blended PBSU increased, possibly indicating that the amorphous PVPh might reside mainly in the interlamellar region of PBSU.     

Polymerization of butadiene with tii4-Al(i-Bu)3 Catalyst: Part II: Kinetic model development

Expressions for conversions, Mn and Mw have been derived for the proposed kinetic scheme for the polymerization of butadiene using Til₄ — Al(i-Bu)₃ as catalyst. The rate constants k_p, k_ta and k_d and the active sites were estimated from experimental data of conversion and molecular weight averages. The logarithm of both k_p and k_ta are linearly related to Al/Ti ratio. On the other hand, k_d and C_o appear to be uncorrelated with the reaction variables studied in this investigation. The activation energy for propagation reaction was found to be 12.05 ± 1.31 which agrees well with those reported previously. The small difference in the activation energies for k_p and k_ta accounts for the independence of the molecular weight of the polymer on the reaction temperature.     

Master curve of crystal growth rate and its corresponding state in polymeric materials

The temperature dependence of linear crystal growth rate (G) for various polymers shows a bell shape with the maximum growth rate (G_max). The G_max shows remarkable molecular weight dependence. The G_max was formulated on the basis of a crystallization theory, both for Arrhenius and WLF expressions in the molecular transport term. The plots of the reduced growth rate (G/G_max) against the reduced temperature (T/T_cmax) for a given polymer showed a single master curve without molecular weight dependence. The ratio of G₀/G_max gave a constant value for each polymer, indicating a material constant. On the basis of G_max for many polymers, a universal master curve was observed when the ratio of ln(G/G_max)/ln(G₀/G_max) was plotted against the reduced temperature (T/T_cmax).     

Synthesis of narrow distribution polytetrahydrofuran

Bulk polymerizations of tetrahydrofuran (THF) have been studied kinetically at reaction temperatures in the range ?10 to +80°C using p-chlorophenyldiazonium hexafluorophosphate initiator. Initiation has been studied to enable selection of a ‘clean’ initiation condition (95°C for 4 min). Factors causing broadening of the molecular weight distribution are discussed, the main causes of such broadening being chain transfer reactions and concurrent initiation with propagation. These could be minimized by using a low reaction temperature (?10°C). Molecular weight distributions were measured by gel permeation chromatography. Propagation rate constants were determined and found to increase with increasing temperature according to an Arrhenius expression giving an activation energy of 51 kJ/mol. The method will produce monodisperse samples of THF polymer over a wide molecular weight range from 5 × 10³ to 10⁶.     

ESR study of the radical polymerization of styrene

Summary The absolute rate constant of propagation (k_p) in styrene polymerization was determined on the basis of ESR detection of the polymer radical in the temperature range of 0 to 130°C. The Arrhenius plot of k_p gave a good linear relationship and the activation energy of the propagation was evaluated to be 39.7 KJ/mol. The termination rate constants over the same temperature range were also obtained by using the k_p values according to the standard kinetics of radical polymerization. Apparent activation energy of the termination was estimated to be 15.6 KJ/mol.     

Effect of molecular weight on spherulitic growth rate of poly(ϵ‐caprolactone) and poly(ϵ‐caprolactone)‐b‐poly(ethylene glycol)

The spherulitic growth rates of a series poly (?‐caprolactone) homopolymers and poly(?‐caprolactone)‐b‐ poly(ethylene glycol) (PCL‐b‐PEG) block copolymers with different molecular weights but narrow polydispersity were studied. The results show that for both PCL homopolymers and PCL‐b‐PEG block copolymers, the spherulitic growth rate first increases with molecular weight and reaches a maximum, then decreases as molecular weight increases. Crystallization temperature has greater influence on the spherulitic growth rate of polymers with higher molecular weight. Hoffman–Lauritzen theory was used to analyze spherulitic growth kinetics and the free energy of the folding surface (σ_e) was derived. It is found that the values of σ_e decrease with molecular weight at low molecular weight level and become constant for high molecular weight polymers. The chemically linked PEG block does not change the values of σ_e significantly. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis of star‐shaped poly(ε‐caprolactone)‐b‐poly(L‐lactide) copolymers: From star architectures to crystalline morphologies

Hexa‐armed star‐shaped poly(ε‐caprolactone)‐block‐poly(L ‐lactide) (6sPCL‐b‐PLLA) with dipentaerythritol core were synthesized by a two‐step ring‐opening polymerization. GPC and ¹H NMR data demonstrate that the polymerization courses are under control. The molecular weight of 6sPCLs and 6sPCL‐b‐PLLAs increases with increasing molar ratio of monomer to initiator, and the molecular weight distribution is in the range of 1.03–1.10. The investigation of the melting and crystallization demonstrated that the values of crystallization temperature (T_c), melting temperature (T_m), and the degree of crystallinity (X_c) of PLLA blocks are increased with the chain length increase of PLLA in the 6sPCL‐b‐PLLA copolymers. On the contrary, the crystallization of PCL blocks dominates when the chain length of PLLA is too short. According to the results of polarized optical micrographs, both the spherulitic growth rate (G) and the spherulitic morphology are affected by the macromolecular architecture and the length of the block chains. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Quiescent crystallization kinetics and morphology of isotactic polypropylene resins for injection molding. I. Isothermal crystallization

The quiescent isothermal crystallization kinetics of polypropylene was studied as a function of molecular weight (M_w), amount of ethene, and amount of maleic anhydride and acrylic acid grafting. Differential scanning calorimetry and polarized light optical microscopy were used to follow this kinetics. It was observed that the linear growth rate, G, decreased with the increase of M_w, but increased with the amount of ethene. In the grafted polymers, as the amount of grafting increased, G decreased. The fold surface free energy, σ_e, was found to increase with the increase in M_w. The heterophasic and grafted polymers had σ_e values higher than the homopolymers. All samples showed spherulitic morphology, except the acrylic acid-grafted polypropylene that showed axialitic morphology. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1159–1176, 1998     

Crystallization of polyformals: 2. Influence of molecular weight and temperature on the morphology and growth rate in poly(1,3-dioxolane)

The morphology and growth rates of crystallized molecular weight fractions of poly(1,3-dioxolane) covering the range M_n = 8 800 to 120 000 have been studied by polarized light microscopy. Two different supermolecular structures, dependent on molecular weight and crystallization temperature have been found. Spherulites are formed after rapid crystallization and a more disordered morphology is formed at the lowest undercoolings but there is a temperature region where both forms are observed. The disordered form appears first and a consecutive spherulitic growth takes place. The crystallization kinetics were analysed over the temperature range 10°C to 36°C. At crystallization temperatures lower than 15°–18°C, the growth rate is linear and only spherulites are found. In the temperature range from 18°C to 36°C a well defined break is observed in the growth rate but the spherulitic growth rate is always higher than that of the irregular form. The growth rate temperature coefficient was studied and the usual plots are not linear in the whole range of crystallization temperatures. For the high crystallization temperature region, the slope is about twice as great as the low crystallization temperature slope. This is the region where regular spherulites are formed. The comparison between dilatometric and growth rate data has shown that the overall rate and growth rate temperature coefficients are the same.     

Spherulitic Morphology and Crystallization Kinetics of Poly(vinylidene fluoride)/Poly(vinyl acetate) Blends

Spherulitic morphology and crystallization kinetics of the blends of poly(vinylidene fluoride) (PVDF) and poly(vinyl acetate) (PVAc) prepared by solution casting films have been investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The results suggested that PVAc was mainly segregated into the interlamellar and/or interfibrillar regions due to the volume-filling spherulitic morphology observed. As for the results of crystallization kinetics, it was found that both the PVDF spherulitic growth rate (G ^PVDF) and the overall crystallization rate constant (k _n ) were depressed with either the addition of PVAc component or the increase of crystallization temperature (T _c). The kinetics retardation was attributed to the decrease in PVDF molecular mobility and dilution of PVDF concentration due to the addition of PVAc, which has a higher glass transition temperature (T _g).     

Quiescent crystallization kinetics and morphology of i‐PP resins for injection molding. II. Nonisothermal crystallization as a function of molecular weight

The quiescent nonisothermal crystallization kinetics of polypropylene resins was studied as a function of their molecular weight, M_w. Differential scanning calorimetry and polarized light optical microscopy were used to follow this kinetics. It was observed that a modified Hoffman and Lauritzen equation could describe with accuracy their nonisothermal behavior. Also it was found that the polypropylene nonisothermal growth rates, G_n, were similar to their corresponding isothermal rates, G, and also decreased with the increase in M_w. The use of a prior isothermal nucleation procedure allowed to obtain data at higher temperatures and to compare these data at higher cooling rates than the ones found in the literature. The morphology of all the samples revealed a fine and radial spherulitic texture. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1733–1740, 1999     

Crystallization studies of semi-crystalline polymers under oscillatory shear using the rheometrics mechanical spectrometer

A method has been developed on the Rheometrics mechanical spectrometer using the eccentric rotating disks mode to study the crystallization kinetics of different semi-crystalline polymers (polyethylene, polypropylene, poly(butylene terephthalate) and Nylon 11) under oscillatory shear. Dynamic shear moduli (storage G′ and loss G″), loss tangent (tan δ), and dynamic viscosity (η′) were simultaneously, monitored during the crystallization process. The onset and completion of crystallization were characterized by the initial rise and final levelling off of G′, while the peak time, of crystallization (t_p) is calculated from the time elapsed between the onset and peak of crystallization which is indicated by the G″ or η′ maximum. In the case of polypropylene, going from a low frequency of ?0.1 rad/s, to higher frequencies of up to 10 rad/s, there is a monotonic decrease in peak time of crystallization (t_p) together with a progressive decrease in spherulitic morphology. The observed acceleration in crystallization is due predominantly to the increase in nucleation rate and orientation of chains in melt crystalline aggregate. The progressive disappearance of the spherulitic morphology is attributed to the disruption of the spherulite superstructure at higher frequencies of shear.     

Power law and scaling for molecular weight dependence of crystal growth rate in polymeric materials

The molecular weight (M) dependence of the linear crystal growth rate (G) and the influence of the super-cooling on the relationship between M and G were studied. The molecular weight dependence of G has been expressed generally as G∝M^α at a given super-cooling. The temperature dependence of G shows a bell shape with the maximum growth rate (G_max). The value of α was −0.5 at the temperature (T_cmax) of G_max. However, the small super-cooling and the small molecular weight gave a large negative value of α. In other words, the value of α was dependent not only on the degree of super-cooling (ΔT) but also on the molecular weight. The effect on α by these two factors (ΔT and M) goes off to zero at T_cmax and α yields to −0.5. G_max can be defined as a characteristic intrinsic value to the crystal growth behavior. The molecular weight dependence of G_max was scaled and expressed as a −0.5 power to molecular weight for all crystalline polymers.     

Mobilities of polymer liquids at constant temperature and at constant volume

Previously developed relationships between isomobility states and equilibrium p-v-T properties of vinyl polymers are extended to predict mobilities, μ, at constant temperature and at constant volume, with poly(vinyl acetate) as an example. At constant volume, μ changes by several orders of magnitude while the ‘internal pressure’ remains constant, suggesting that kinetic energy (temperature) dominates in governing μ. From μ at constant temperature the Vogel parameters, B and T₀, are found to increase with pressure, the former increasing linearly. A new Vogel type equation is developed in which one of the parameters, B_v, depends only on the chemical composition of the polymer. Both μ and its ‘activation energy’ at constant pressure, E_p, are shown to be constant at the glass transition.