Γ-form Crystals Research Articles

Polyvinylidene Fluoride (PVDF) Crystallization Kinetics in an Electric Field

To study the effect of applied electric field on polymer crystallization, the crystallization of polyvinylidene fluoride (PVDF) was observed under modified polarized optical microscopy. The PVDF melts were crystallized based on programmed temperature, changes between two transparent conductive glass electrodes, on which a DC electric field was applied. The observations revealed that without the electric field, crystallizations below 160 °C resulted in only α-form crystals, while, at elevated temperatures, the formation of γ-form crystals also occurred. By applying the electric field at 1.7 kV/cm, γ-form crystals started emerging at the slightly lower temperature of 158 °C. Further examinations showed that both crystals, α-form and γ-form, grew at a greater rate with increasing field strength. A careful calculation of the Avrami parameters supported the data that the electric field enhanced the crystallization kinetics. Careful calculation based on the Laurientz–Hoffmann approach revealed that applying the electric field decreased the required energy for PVDF crystallization. The folding surface free energy of the PVDF crystallization, 1.76 × 10−2 Jm−2, was reduced to 1.57 × 10−2 Jm−2 and 1.43 × 10−2 Jm−2 after applying electric fields of 0.8 and 1.7 kVcm−1, respectively. We suggest that the electric field promoted the polymer chain alignment during the crystallization; as a result, it accelerated the polymer crystallization and lowered the energy requirement for crystallization.

The phase transition of polyamide 6 with pre-stretching process at different temperatures

The temperature and strain fields are two key factors in the regulation of fibrous aggregate structure. In this paper, plate specimens of polyamide 6 were prepared by compression molding method. The oriented polyamide 6 plates were systematically analyzed from aspects of mechanical properties, thermal properties, crystal structure and crystal morphology. The maximum tensile strength and elastic modulus of polyamide 6 plate appeared at 120 °C. The stretching process induced the formation of a more thermal stable α-form crystals. With the increase of stretching temperature, α-form crystals transformed into γ-form crystals gradually. The crystal chips transformed into fibrils during the stretching process. The structural evolution model of materials under the temperature and strain fields was established.

Fast Continuous Non-Seeded Cooling Crystallization of Glycine in Slug Flow: Pure α-Form Crystals with Narrow Size Distribution

Glycine has been widely used as pharmaceutical excipients and synthesis reagents, and commercial glycine has a significant amount of aggregation and wide particle size distribution. A simple but reproducible process for generating uniform glycine crystals is always desired for both product quality and process efficiency purposes. Continuous cooling crystallization of glycine has been carried out in air-liquid slug flow in millimeter ID tubing, starting from solution without using seeds. Slugs were formed by combining air and liquid streams, then went through the crash cooling zone of varying lengths (tubing length in contact with ice bags). The operational boundaries of crash cooling times were evaluated: natural cooling (lower bound, no crash cooling), maximum cooling time for pure α-form without aggregation (upper bound), and beyond upper bound. Non-aggregating pure α-form glycine crystals were continuously generated within ~ 10 min, feasible from multiple conditions (combinations of crashing cooling time and starting concentration). When crash cooling time further increases (while maintaining the starting concentration), crystal aggregations and/or γ-form crystals could appear. Reducing starting concentration can allow longer crash cooling time without widening product crystal size distribution or reducing crystalline form purity. At proper conditions, even natural cooling in slugs can nucleate and grow non-aggregated pure α-form crystals. All cooling conditions carried out in slug flow generally minimize needle-shaped crystals compared with corresponding batches. Glycine crystals of α-form and narrow size distribution can be continuously generated within 10 min from cooling crystallization in millimeter-sized slug flow, without using external seeds nor adding solvent/additives. And, the operational boundaries of crash cooling time (at proper starting concentrations) for pure α-form non-aggregating product crystals are identified.

Polyamide 6/Poly(vinylidene fluoride) Blend-Based Nanocomposites with Enhanced Rigidity: Selective Localization of Carbon Nanotube and Organoclay.

Polyamide 6 (PA6)/poly(vinylidene fluoride) (PVDF) blend-based nanocomposites were successfully prepared using a twin screw extruder. Carbon nanotube (CNT) and organo-montmorillonite (30B) were used individually and simultaneously as reinforcing nanofillers for the immiscible PA6/PVDF blend. Scanning electron micrographs showed that adding 30B reduced the dispersed domain size of PVDF in the blend, and CNT played a vital role in the formation of a quasi-co-continuous PA6-PVDF morphology. Transmission electron microscopy observation revealed that both fillers were mainly located in the PA6 matrix phase. X-ray diffraction patterns showed that the presence of 30B facilitated the formation of γ-form PA6 crystals in the composites. Differential scanning calorimetry results indicated that the crystallization temperature of PA6 increased after adding CNT into the blend. The inclusion of 30B retarded PA6 nucleation (γ-form crystals growth) upon crystallization. The Young’s and flexural moduli of the blend increased after adding CNT and/or 30B. 30B exhibited higher enhancing efficiency compared with CNT. The composite with 2 phr 30B exhibited 21% higher Young’s modulus than the blend. Measurements of the rheological properties confirmed the development of a pseudo-network structure in the CNT-loaded composites. Double percolation morphology in the PA6/PVDF blend was achieved with the addition of CNT.

Structure and properties of PA6-66/γ-aminopropyltriethoxysilane-modified clay nanocomposites prepared by in situ polymerization

Abstract In this study, PA6-66/γ-aminopropyltriethoxysilane-modified clay nanocomposites were prepared by in situ polymerization. It was found that the γ-aminopropyltriethoxysilane was chemically grafted onto clay successfully, and the covalent bond was formed between the clay and polymer chains. The transmission electron microscopy (TEM) and X-ray diffraction (XRD) results indicated that intercalated and exfoliated nanocomposites were obtained. The PA6-66 nanocomposites exhibited improved mechanical performance compared to that of neat PA6-66. Most importantly, the PA6-66 nanocomposites showed significantly improved toughness. In comparison with neat PA6-66, the rupture stress and elongation at the break of the nanocomposite with only 0.5 wt% clay increased 91.9% and 91.8%, respectively. The excellent toughness of PA6-66 nanocomposites should be mainly ascribed to the combined effects of strong polymer-clay interaction, the intercalated-exfoliated structures of clay, refined crystalline, formation of γ-form crystals, and decreased crystallinity of PA6-66.

Rheology, Crystallization, Mechanical and Barrier Properties of Polyamide 6/66 Nanocomposites with Exfoliated Organoclays

ABSTRACTNylon copolymer/clay (NC) nanocomposites were prepared using PA6/66 as a matrix and organoclay as a nanofiller through a two-step melt-compounding method. It was shown that the organoclay flakes were well exfoliated and dispersed in the PA6/66 matrix. With increasing content of organoclay, the apparent shear viscosity and the entrance pressure drop of the NC nanocomposites decreased whereas the corresponding shear activation energy increased, suggesting that the NC nanocomposites were suitable to be used in shear-flow rather than extension-flow related processes. Investigations of the crystallization behaviors of the NC nanocomposites indicated that the organoclay addition was capable of facilitating the γ-form crystal formation, which is suggested to be due to the restriction effect of the organoclay on the PA6/66 chain motion during the crystallization. Compared to the neat PA6/66, the tensile strength and elongation at break of the NC nanocomposites were both enhanced at an appropriate content of the organoclay. In addition, the NC nanocomposites exhibited enhanced barrier properties due to the high specific surface area and the homogeneous dispersion of the organoclay.

Revisiting the Thermal Transition of β-Form Polyamide-6: Evolution of Structure and Morphology in Uniaxially Stretched Films

Structure and morphology evolution of the uniaxially stretched polyamide-6 (PA6) film with the β-form upon heating were investigated mainly by synchrotron two-dimensional (2D) wide-angle X-ray diffraction and small-angle X-ray scattering. For comparison, thermal transitions of the oriented PA6 samples with the α- and γ-form were also monitored, which undergo “incomplete Brill transition” and direct melting, respectively. Using the results of oriented α- and γ-PA6 as the references, we confirm that the stretched β-PA6 is mesomorphic, which can be viewed as a solid mesophase with smectic B-like structure. We identify that upon heating the stretched β-PA6 reorganizes dominantly into γ-form crystal with the chain orientation unchanged, accompanied by the formation of a little amount of α-PA6 crystallites. Further heating to above the melting temperature of γ-PA6, the α-PA6 crystals grow through a recrystallization process. The lamellae resulting from reorganization exhibit a distribution of orientations, and the α-PA6 lamellae formed at high temperatures have the lamellar basal surface normal parallel to the stretched direction. We consider that the abundant hydrogen bonds in the stretched β-PA6 film construct a network, providing the confinement effect to reduce the chain mobility and thus favor the formation of γ-form. The lamellae with the basal surface normal tilted relative to the stretched direction can also be attributed to the hydrogen-bonded network of oriented chains.

Counits Content and Stretching Temperature-Dependent Critical Stress for Destruction of γ Crystals in Propylene-Ethylene Random Copolymers.

Tensile deformation behavior of three random propylene–ethylene copolymers with the same molecular weight and different contents of counit was investigated at different temperatures from room temperature to close to melting point via tensile tests, step-cycle tests, and in situ wide-angle X-ray diffraction techniques. Upon stretching, the original crystalline lamellae must be destroyed, generating new highly oriented ones. A critical stress has been suggested, under which the original crystallites can be destructed. The propylene–ethylene copolymer samples in pure γ-form transformed gradually into α-form during tensile stretching. This crystalline transition proceeded via a destruction (melting) of the original γ-form crystals followed by recrystallization of the freed polymeric chain segments into α-form along stretching direction. This result provides a marker for investigating the critical stress mentioned above. Such critical stresses triggering the destruction of γ-form crystals for the propylene–ethylene copolymers of different ethylene counit contents were successfully calculated. It turned out that this critical stress depended on the ethylene counit content and stretching temperature. Samples with less ethylene counits show higher critical stress because of a lower degree of insertion of the ethylene counits into the crystalline unit cell than samples with higher ethylene counit content. The critical stresses remained constant when the samples were stretched at low-temperature region, whereas they decreased significantly at high stretching temperatures close to the melting points due to strong thermal distortion of the crystalline lattices, making the crystallites less stable.

Structure evolution of polyamide (11)’s crystalline phase under uniaxial stretching and increasing temperature

Thermal processing of polyamide influences the internal crystalline structure and thereafter the post product mechanical performance. In this article, the crystalline transition of polyamide-11 (PA11) plate under uniaxial stretching and increasing temperature was investigated systematically using in-situ synchrotron X-ray technique. It was discovered that the lamellar slippage, fragmentation and recrystallization occurred in sequence under increasing temperature. In detail, the crystal of PA11 plate was stretched with a transition from triclinic α-form to mesomorphic phase at 25 °C. For the thermally activated γ-form crystals, crystal transition was inhibited when temperature was increased up to 160 °C. The melt-recrystallization was inclined to take place at large tensile strains. This work enhances the research significance of the thermal processing of polyamide and provides a theoretical method to improve the high performance of polyamide products.

Structure and Performance of PP Porous Membrane Prepared with Adipic Acid and NA-40 as Nucleating Agent via TIPS

Polypropylene (PP) membranes were respectively prepared using adipic acid (APA) and Sorbitol (NA-40) as nucleating agent via thermally induced phase separation (TIPS) method. The effects of nucleating agent content and cooling temperature on the structure and performance of membrane were investigated using scanning electron microscopy (SEM), wide angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). WAXD spectrogram indicates that three kinds of α, β and γ-form crystal were formed in this preparation process and the relative content of β-form crystal in membrane prepared by NA-40 system is higher than that of membrane formed by adipic acid. SEM images show that porous structure and cellular structure were observed on the surface and cross-section of membrane. The water flux, tensile strength and elongation increase with the addition of nucleating agent content and decrease with cooling temperature rising. This paper aims to choose proper nucleating agent NA-40 and coagulation temperature to improve the properties of PP membranes.

Crosslinked P(VDF-CTFE)/PS-COOH nanocomposites for high-energy-density capacitor application

High-capacity or high-power-density capacitors are being actively investigated for portable electronics, electric vehicles, and electric power systems. The dielectric nanocomposite with a small loading of carboxylic polystyrene (PS-COOH) nanoparticles in poly(vinylidene fluoride-chlorotrifluoroethylene) [P(VDF-CTFE)] matrix, followed by chemical crosslinking has been described. Combination of these two methods significantly improved the capacity of electric energy storage at low electric field. Specially, the nanocomposite with 2 wt % nanoparticles and 15 wt % crosslinking agent achieved a dielectric constant of 17.2 and a discharged energy density of 17.5 J/cm3 (4.9 Wh/L) at an electric field as high as 324 MV/m, while corresponding values for pristine P(VDF-CTFE) are 9.6 and 13.3 J/cm3 (3.7 Wh/L), respectively. Fundamental physics underlying the enhancement in the performance of the nanocomposites with respect to P(VDF-CTFE) is illustrated by solid-state 19F nuclear magnetic resonance of direct excitation or 19F{1H} cross polarization. It revealed different dynamics behavior between crystalline/amorphous regions, and PS-COOH nanoparticles favored the formation of polar γ-form crystals. Small-angle X-ray scattering studies revealed the contribution of the interface to the extraordinary storage of electric energies in the nanocomposites. This approach provided a facile and straightforward way to design or understand PVDF-based polymers for their practical applications in high-energy-density capacitors. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 1160–1169

Assembly of polyamide 6 nanotube arrays with ordered patterns and the crystallization behavior

Highly ordered arrays of polyamide 6 (PA6) nanotubes were successfully prepared using photolithography via polymer solution wetting the anodic aluminum oxide (AAO) templates. The samples were examined by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD). The crystal structure and the crystallinity of the samples were influenced by the presence of nanopores in the AAO template. Nanopore-induced crystal transformation from the α-form to the γ-form of PA6 was confirmed by XRD, and the formation of γ-form crystal was enhanced by the presence of nanopores in the AAO template. The formation of γ-form crystal was also discussed. These results indicated that nanopores provided favorable conditions for the crystallization of γ phase.

Structure-property relationship of supramolecular ferroelectric [H-66dmbp][Hca] accompanied by high polarization, competing structural phases, and polymorphs.

Three polymorphic forms of 6,6'-dimethyl-2,2'-bipyridinium chloranilate crystals were characterized to understand the origin of polarization properties and the thermal stability of ferroelectricity. According to the temperature-dependent permittivity, differential scanning calorimetry, and X-ray diffraction, structural phase transitions were found in all polymorphs. Notably, the ferroelectric α-form crystal, which has the longest hydrogen bond (2.95 Å) among the organic acid/base-type supramolecular ferroelectrics, transformed from a polar structure (space group, P21) into an anti-polar structure (space group, P21/c) at 378 K. The non-ferroelectric β- and γ-form crystals also exhibited structural rearrangements around hydrogen bonds. The hydrogen-bonded geometry and ferroelectric properties were compared with other supramolecular ferroelectrics. A positive relationship between the phase-transition temperature (TC ) and hydrogen-bond length (<d>) was observed, and was attributed to the potential barrier height for proton off-centering or order/disorder phenomena. The optimized spontaneous polarization (Ps ) agreed well with the results of the first-principles calculations, and could be amplified by separating the two equilibrium positions of protons with increasing <d>. These data consistently demonstrated that stretching <d> is a promising way to enhance the polarization performance and thermal stability of hydrogen-bonded organic ferroelectrics.

Molecular self-assembly of nylon-12 nanorods cylindrically confined to nanoporous alumina.

Molecular self-assembly of nylon-12 rods in self-organized nanoporous alumina cylinders with two different diameters (65 and 300 nm) is studied with transmission electron microscopy (TEM) and wide-angle X-ray diffraction (WAXD) in symmetrical reflection mode. In a rod with a 300 nm diameter, the tendency of the hydrogen-bonding direction of a γ-form crystal parallel to the long axis of the rod is not clear because of weak two-dimensional confinement. In a rod with a diameter of 65 nm, the tendency of the hydrogen-bonding direction of a γ-form crystal parallel to the long axis of the rod is more distinct because of strong two-dimensional confinement. For the first time, selected-area electron diffraction (SAED) is applied in a transmission electron microscope to a polymer nanorod in order to determine the hydrogen-bond sheet and lamellar orientations. Results of TEM-SAED and WAXD showed that the crystals within the rod possess the γ-form of nylon-12 and that the b axis (stem axis) of the γ-form crystals is perpendicular to the long axis of the rod. These results revealed that only lamellae with 〈h0l〉 directions are able to grow inside the nanopores and the growth of lamellae with 〈hkl〉 (k ≠ 0) directions is stopped owing to impingements against the cylinder walls. The dominant crystal growth direction of the 65 nm rod in stronger two-dimensional confinement is in between the [-201] and [001] directions due to the development of a hydrogen-bonded sheet restricted along the long axis of the rod.

A micromechanical model taking into account the contribution of α- and γ-crystalline phases in the stiffening of polyamide 6-clay nanocomposites: A closed-formulation including the crystal symmetry

A clay-induced crystal transformation has been widely pointed out in semi-crystalline polymer–clay nanocomposites, from the α-form to the γ-form in the particular case of polyamide 6 (PA6). The proposition of a predictive model taking explicitly into account the polymer crystalline structure is still needed for a reliable prediction of the structure–property relationship and for a better understanding of the reinforcement mechanism in such systems. The aim of this paper is to present an approach issued from the continuum-based micromechanical framework using self-consistency condition to predict the overall stiffness of PA6-clay nanocomposites. Besides the effect of clay particle characteristics, the micromechanical model introduces the contribution of α- and γ-form crystals in the overall stiffness by considering the PA6 matrix as a heterogeneous medium containing distinct amorphous and crystalline phases. A closed-formulation of the micromechanical model is derived using the Walpole spectral decomposition of the stiffness tensors for the two monoclinic crystalline phases. Two possible representations of the microstructure are considered: the first one considers that all the phases are independent and the second one that the γ-crystalline phase constitutes an interphase region around clay particles. The micromechanical model using the two morphological representations is used to predict the overall stiffness of PA6 nanocomposites reinforced with montmorillonite clay (adjusted from 1wt% up to 20wt%) for which the polymer crystalline structure was characterized by infrared spectroscopy and calorimetry. The respective role of clay particles and of two crystalline species in the stiffening of exfoliated and intercalated PA6-clay nanocomposites is discussed with respect to the micromechanical model.

Substrate effects on the surface properties of nylon 6

Thin nylon 6 films spin coated onto different substrates were characterized by wide-angle X-ray scattering (WAXS), Fourier transformation infrared (FTIR) spectroscopy, FTIR trichroic analysis and water contact angle (CA) measurements. The morphology and hydrophilicity of the nylon 6 surface were found to be greatly influenced by the nature of the substrate. The film surface contained primarily α-form crystals when it was prepared using hydrophobic substrates. This film was more hydrophobic. However, for hydrophilic substrates, the film surface comprised mainly γ-form crystals and demonstrated greater hydrophilicity. FTIR trichroic analysis of the NH stretching vibration mode revealed that the presence of a hydrophilic substrate caused the NH stretching bonds on the film surface to align preferentially in the direction perpendicular to the surface. Such effects were attributed to molecular interactions between the NH bonds of the polymer and SiO bonds of the hydrophilic substrate.

Graphene oxide–polyamide 6 nanocomposites produced via in situ polymerization

Single layer graphene oxide (GO)–polyamide 6 (PA6) nanocomposites were produced via the in situ polymerization of ∊-caprolactum dissolved in a water-based dispersion of single layer GO. As prepared GO and nanocomposites containing 0, 0.035, 0.076, 0.44 and 0.65 wt% GO in PA6 were characterized using transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), Raman thermal analysis and tensile testing. XPS, AFM and TEM analyses confirmed that the modified Hummers method used to prepare the GO resulted in sheets of oxidized single layer graphene. It was observed using AFM that the in situ polymerization resulted in an efficient poly chain grafting and a reduction in the lateral dimensions of the sheets. The GO/PA6 nanocomposites showed an increased degradation temperature relative to neat PA6, which is an indicative of high levels of interfacial interaction and dispersion. It was observed that the addition of GO reduced the average PA6 molecular weight and acted as nucleation agent for α-form crystallinity while suppressing the formation of γ-form crystals. Mechanical reinforcement was also observed, with a tensile strength of 60.6 MPa recorded for PA6, rising incrementally with increased GO loading to 64.9 MPa at 0.65 wt%.

Structural studies of electrospun nylon 6 fibers from solution and melt

Nylon 6 (N6) fibers have been fabricated via two different electrospinning schemes, from solution of N6 and formic acid at room temperature as well as from N6 melt at elevated temperature. The crystal structures of electrospun N6 fibers from solution and melt, and the annealing effect on the structures were studied by using various techniques. Combined analysis of the differential scanning calorimetry (DSC) at various heating rates, temperature-dependent X-ray diffraction (XRD), and Fourier-transform infrared (FTIR) spectroscopy indicates that N6 fibers from melt predominantly exhibit the meta-stable γ-crystalline forms and low molecular orientation, while solution electrospun fibers from slowly evaporating solvent show both α- and γ-form crystals and higher degree of molecular orientation. At high annealing temperature, the meta-stable γ-crystals in melt electrospun fibers easily transform into thermodynamically stable α-form crystals, while crystals in solution electrospun fibers exhibit higher thermal stability. Nonisothermal modeling and in-situ measurements of jet temperature indicate that rapid quenching due to enhanced heat transfer by electrohydrodynamically driven air flow near the jet is responsible for the less stable γ-crystals and lower degree of molecular orientation in melt electrospun fibers.

Characterization of nylon 6/ABS blends with and without a maleated polybutadiene as compatibilizer

The physical properties of nylon 6/poly(acrylonitrile-butadiene-styrene) terpolymer (ABS) blends using a maleated polybutadiene (denoted PB-g-MA) as compatibilizer were investigated. The morphology results reveal that ABS domain sizes decrease with an increasing compatibilizer content, suggesting the good interaction between the nylon 6 matrix and the ABS dispersed phase. Cooling conditions and compatibilizer contents strongly affect the crystalline structure of nylon 6, as determined from X-ray diffraction and non-isothermal crystallization thermal analyses. The coexistence of α- and predominantly γ-form crystals for the 10 phr compatibilized blends was observed. Isothermal crystallization kinetics suggests that the introduced compatibilizer impeded the growth rate of the crystals, especially for the higher compatibilizer content. The compatibilizer was beneficial in enhancing the thermal stability of the blends.

CO2-induced Crystallization of Isotactic Polypropylene by Annealing Near Its Melting Temperature

CO2-induced crystallization of isotactic polypropylene (iPP) by annealing had been studied using differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS). The iPP before annealed was in α-form and amorphous states. At lower temperatures by CO2 isothermal treatments, iPP chains crystallized from the amorphous phase and only one crystal form, i.e., α-form, was observed. At higher temperatures by CO2 isothermal treatments, both crystallization from the amorphous phase and thickening of existing crystal lamellae were observed. Moreover, light γ-form crystal appeared in the treated iPP. The crystalline lamellar thickness of iPP annealed at different CO2 pressures had been determined. Using the Gibbs–Thomson plot method, the equilibrium melting temperature was found to be 187.6°C.