Synchrotron investigation on the sheared structure evolution of syndiotactic polypropylene crystallization process

The final structure of molten syndiotactic polypropylene (sPP) sheared under different conditions was investigated by synchrotron small-angle x-ray scattering (SAXS) and wide-angle x-ray diffraction (WAXD) techniques to elucidate the shear effects on sPP crystalline structure. The results obtained from the WAXD show that there is no variation on crystalline form but a little difference on the orientation of the 200 reflection. The SAXS data indicate that the lamellar thickness and long period have not been affected by shear but the lamellar orientation is dependent on shear. The experimental data of sPP crystallization from sheared melt may indicate a mesophase structure that is crucial to the shear effects on the final polymer multiscale crystalline structures.

Study on the formation of beta-crystal during the crystallization process of polypropylene reactor granule

A notable amount of PP beta-crystal (30%, by X-ray diffraction pattern) has been found in the PP samples as polymerized at normal static isothermal crystallization conditions without using any extra nucleating agents. Existence of catalyst residues in the sample is decisive, which slows down the crystallization rate facilitating the formation of beta-form spherulites. Comparatively, high molecular weight PP favors the formation of beta-form spherulites, deducting from no beta-crystal detected in the degraded samples. Finally, high isotacticity is also required for obtaining qualitative beta-form spherulites, demonstrated by increased beta-crystal content after removal of weak crystalline fraction of the sample.

Thermal stability, crystallization, structure and morphology of syndiotactic 1,2-polybutadiene/organoclay nanocomposite

Syndiotactic 1,2-polybutadiene/organoclay nanocomposites were prepared and characterized by thermogravimetry analysis (TGA), X-ray diffraction (XRD), polarized optical microscopy (POM), and differential scanning calorimetry (DSC), respectively. The XRD shows that exfoliated nanocomposites are formed dominantly at lower clay concentrations (less than 2%), at higher clay contents intercalated nanocomposites dominate. At the same time, the XRD indicates that the crystal structures of sPB formed in the sPB/organoclay nanocomposites do not vary, only the relative intensity of the peaks corresponding to (0 1 0) and (2 0 0)/(1 1 0) crystal planes, respectively, varies. The DSC and POM indicate that organoclay layers can improve cooling crystallization temperature, crystallization rate and reducing the spherulite sizes of sPB. TGA shows that under argon flow the nanocomposites exhibit slight decrease of thermal stability, while under oxygen flow the resistance of oxidation and thermal stability of sPB/organoclay nanocomposites were significantly improved relative to pristine sPB. The primary and secondary crystallization for pristine sPB and sPB/organoclay (2%) nanocomposites were analyzed and compared based on different approaches.

Non-isothermal crystallisation kinetics of polyamide 6/mesoporous silica nanocomposites

Non-isothermal crystallisation kinetics of a polyamide 6/mesoporous silica nanocomposite (PA6-MS) has been investigated by differential scanning calorimetry (DSC) at different cooling rates. Mandelkern, Jeziorny-Ziabicki and Ozawa methods were applied to describe this crystallisation process. The analyses show that the mesoporous silica particles act as nucleating agents in the composite and that the Avrami exponent n varies from 3.0 to 4.6. The addition of mesoporous silica influenced the mechanism of nucleation and the growth of polyamide 6 (PA6) crystallites.

Thermal and crystallization behaviors of polyethylene blends synthesized by binary late transition metal catalysts combinations

A series of reactor blends of linear and branched polyethylenes have been prepared, in the presence of modified methylaluminoxane, using a combination of 2,6-bis[1(2,6-dimethyphenylimino) pyridyl]-cobalt(II) dichloride (1), known as an active catalyst for producing linear polyethylene, and [1,4-bis(2,6-diidopropylphenyl)] acenaphthene diimine nickel(II) dibromide (2), which is active for the production of branched polyethylene. The polymerizations were performed at various levels of catalyst feed ratio at 10 bar. The linear correlation between catalyst activity and concentration of catalyst 2 suggested that the catalysts performed independently from each other. The weight-average molecular weights ((M) over bar (w)), crystalline structures, and phase structures of the blends were investigated, using a combination of gel permeation chromatography, differential scanning calorimetry, wide-angle X-ray diffraction, and small angle X-ray scattering techniques. It was found that the polymerization activities and MWs and crystallization rate of the polymers took decreasing tendency with the increase of the catalyst 2 ratios, while melting temperatures (T-m), crystalline temperatures (T,), and crystalline degrees took decreasing tendency. Long period was distinctly influenced by the amorphous component concentration.

Effect of copolymerized ethylene unit on the crystallization behavior of poly(propylene-co-ethylene)s

The crystallization behavior of two kinds of commercial poly(propylene-co-ethylene)s (PPE1, PPE2) with similar average molecular weight and molecular weight distribution, isotacticity and copolymerized ethylene unit content and their fractions was investigated by differential scanning calorimetry (DSC), transmission electron microscopy (TEM) and polarized optical microscopy (POM) techniques. The results indicate that the PPE1 isothermally crystallized films possess thicker and less cross-hatched lamellar structure than those of the PPE2. As for the fractionated samples, the thin films of low temperature (less than or equal to 90 degreesC) fractions (PPE1-80, PPE2-80) of both PPE1 and PPE2 exhibit similar crystallization behavior, while for the high temperature ( greater than or equal to 95 degreesC) fractions (PPE1-108, PPE2-108), the crystalline morphology has marked differences. Compared with PPE2-108, the PPE1-108 isothermally crystallized thin films possess thicker lamellae and less crosshatched lamellar structure, while for the fibrous crystal number, the former is less than that of the latter. The main reason to create the crystallization behavior differences between the two PPEs and their fractions is due to the effect of molecular chain structure, i.e. the different distribution of copolymerized ethylene unit in polypropylene chains.

Crystallization kinetics and morphology of nylon 1212

The isothermal and non-isothermal crystallization processes of nylon 1212 were investigated by polarized optical microscopy. The crystal growth rates of nylon 1212 measured in isothermal conditions at temperatures ranged from 182 to 132 degreesC are well comparable with those measured by non-isothermal procedures (cooling rates ranged from 0.5 to 11 degreesC/min). The kinetic data were examined with the Hoffman-Lauritzen nucleation theory on the basis of the obtained values of the thermodynamic parameters of nylon 1212. The classical regime I --> II and regime II --> III transitions occur at the temperatures of 179 and 159 degreesC, respectively. The crystal growth parameters were calculated with (100) plane assumed to be the growth plane. The regime I --> II --> III transition is accompanied by a morphological transition from elliptical-shaped structure to banded spherulite and then non-banded spherulite. The development of morphology during isothermal and non-isothermal processes shows a good agreement.

Primary and secondary crystallization kinetic analysis of nylon 1212

The isothermal and non-isothermal melt-crystallization kinetics of nylon 1212 were investigated by differential scanning calorimetry. Primary and secondary crystallization behaviors were analysed based on different approaches. The results obtained suggested that primary crystallization under isothermal conditions involves three-dimensional spherulite growth initiated by athermal nucleation, while under non-isothermal conditions, the mechanism of primary crystallization is more complex. Secondary crystallization displays a lower-dimensional crystal growth, both in the isothermal and non-isothermal processes. The crystallite morphology of nylon 1212, isothermally crystallized at various temperatures, was observed by polarized optical microscopy. The activation energies of crystallization under isothermal and non-isothermal conditions were also calculated based on different approaches.

Influence of shear on polypropylene crystallization kinetics

Isothermal crystallization kinetics under shear in the melt of iPP was investigated by optical microscopy. It appears that shearing from 200 to the crystallization temperatures enhanced the kinetics, but the shear effect was not obvious if the melt of iPP was sheared only at 200. The experiment results show that relaxation plays an important role during crystallization, and that spherulite growth rates increased with shear rates and were governed by relaxation. The effect of flow on the crystallization kinetics can be understood by considering that the increase of the degree of order due to flow results is an effective change of the melt free energy. The Laurizen-Hoffman theory and the DE-IAA model were used to describe the shear-induced crystallization kinetics of iPP excellently.

Crystallization and ring-banded spherulite morphology of poly(ethylene oxide)-block-poly(epsilon-caprolactone) diblock copolymer

The crystallization behavior of crystalline-crystalline diblock copolymer containing poly(ethylene oxide) (PEO) and poly(epsilon-caprolactone) (PCL), in which the weight fraction of PCL is 0.815, has been studied via differential scanning calorimeter (DSC), wide-angle X-ray diffraction (WAXD), and polarized optical microscopy (POM). DSC and WAXD indicated that both PEO and PCL blocks crystallize in the block copolymer. POM revealed a ring-banded spherulite morphology or the PEO-b-PCL diblock copolymer.

Crystallization kinetics in shearing-induced oriented and stretched poly(ethylene oxide)

Isothermal crystallization kinetics in the melting of poly(ethylene oxide) (PEO) were investigated as a function of the shear rate and crystallization temperature by optical microscopy. The radial growth rates of the spherulites are described by a kinetics equation including shearing and relaxation combined effects and the free energy for the formation of a secondary crystal nucleus. The free-energy difference between the liquid and crystalline phases increased slightly with rising shearing rates. The experimental findings showed that the influence of the relaxation of PEO, which is related to the shear-induced orientation and stretch in a PEO melt, on the rate of crystallization predominated over the influence of the shearing. This indicated that the relaxation of PEO should be more important so that the growth rates increase with shearing, but it was nearly independent of the shear rate within the measured experimental range.

Study of the synthesis, crystallization, and morphology of poly(ethylene glycol)-poly(is an element of-caprolactone) diblock copolymers

Poly(ethylene glycol) -poly(epsilon-caprolactone) diblock copolymers PEG-PCL were synthesized by ring-opening polymerization of c-caprolactone using monomethoxy poly(ethylene glycol) as the macroinitiator and calcium ammoniate as the catalyst. Obvious mutual influence between PEG and PCL crystallization was studied by altering the relative block length. Fixing the length of the PEG block (M-n = 5000) and increasing the length of the PCL block, the crystallization temperature of the PCL block rose gradually from I to about 35 degreesC while that of the PEG block dropped from 36 to -6.6 degreesC. Meanwhile, the melting temperature of the PCL block went up from 30 to 60 degreesC, while that of the PEG block declined from 60 to 41 degreesC. If the PCL block was longer than the PEG block, the former would crystallize first when cooling from a molten state and led to obviously imperfect crystallization of PEG and vice versa. And they both crystallized at the same temperature, if their weight fractions were equal. We found that the PEG block could still crystallize at -6.6 degreesC even when its weight fraction is only 14%. A unique morphology of concentric spherulites was observed for PEG5000-PCL5000.

Composition dependence of the crystallization behavior and morphology of the poly(ethylene oxide)-poly(epsilon-caprolactone) diblock copolymer

The crystallization behavior and morphology of the crystalline-crystalline poly(ethylene oxide)-poly(epsilon-caprolactone) diblock copolymer (PEO-b-PCL) was studied by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), Fourier transform infrared spectroscopy (FTIR), small-angle X-ray scattering (SAXS), and hot-stage polarized optical microscope (POM). The mutual effects between the PEO and PCL blocks were significant, leading to the obvious composition dependence of the crystallization behavior and morphology of PEO-b-PCL. In this study, the PEO block length was fixed (M-n = 5000) and the weight ratio of PCL/PEO was tailored by changing the PCL block length. Both blocks could crystallize in PEO-b-PCL with the PCL weight fraction (WFPCL) of 0.23-0.87. For the sample with the WFPCL of 0.36 or less, the PEO block crystallized first, resulting in the obvious confinement of the PCL block and vice versa for the sample with WFPCL of 0.43 or more. With increasing WFPCL, the crystallinity of PEO reduced continuously while the variation of the PCL crystallinity exhibited a maximum. The long period of PEO-b-PCL increased with increasing WFPCL from 0.16 to 0.50 but then decreased with the further increase of WFPCL due to the interaction of the respective variation of the thicknesses of the PEO and PCL crystalline lamellae.

Nonisothermal crystallization behavior of the poly(ethylene glycol) block in poly(L-lactide)-poly(ethylene glycol) diblock copolymers: Effect of the poly(L-lactide) block length

The confined crystallization behavior, melting behavior, and nonisothermal crystallization kinetics of the poly(ethylene glycol) block (PEG) in poly(L-lactide)poly(ethylene glycol) (PLLA-PEG) diblock copolymers were investigated with wideangle X-ray diffraction and differential scanning calorimetry. The analysis showed that the nonisothermal crystallization behavior changed from fitting the Ozawa equation and the Avrami equation modified by Jeziorny to deviating from them with the molecular weight of the poly(L-lactide) (PLLA) block increasing. This resulted from the gradual strengthening of the confined effect, which was imposed by the crystallization of the PLLA block. The nucleation mechanism of the PEG block of PLLA15000-PEG5000 at a larger degree of supercooling was different from that of PLLA2500-PEG5000, PLLA5000-PEG5000, and PEG5000 (the numbers after PEG and PLLA denote the molecular weights of the PEG and PLLA blocks, respectively). They were homogeneous nucleation and heterogeneous nucleation, respectively.

Miscibility and crystallization behavior of PBT/epoxy blends

The 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 K, 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, sigma(e) = 101.7-58.0 x 10(-3) J/m(2), 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.