Phase Ordering and Crystallization Kinetics in Ultrathin Poly(ethylene oxide)/Poly(methyl methacrylate) Blend Films

Crystallization in ultrathin Poly(Ethylene Oxide)/Poly(Methyl Methacrylate) (PEO/PMMA) blend films with thickness of ca. 10 nm was investigated by means of microscopic and in situ spectroscopic methods. It was revealed that the blend films undergo a phase ordering in a humid atmosphere before or during crystallization, with PEO de-mixing with PMMA and segregating to the free film interface on the PMMA layer. The de-mixed PEO chains crystallize into a fractal-like morphology by a diffusion-limited process, and the crystal growth is 1-dimensional with Avrami exponent n ≈ 1, resulting in flat-on crystal lamellae with the PEO chains oriented normal to the film plane.     

WAXS studies on crystalline behavior of polymethyl methacrylate-polyethylene oxide graft copolymers and their ionic complexes

A graphical multiple-peak resolution method for wide-angle x-ray scattering (WAXS) patterns is described and used to estimate the apparent crystallinities relative to the entire sample (Xca) in polymethyl methacrylate-polyethylene oxide graft copolymers (PMMA-g-PEO) and their ionic complexes with LiClO₄, KSCN and FeCl₂. The crystallinities (Xcg) and crystallite sizes (L ₁₂₀) in the PEO graft component, alone, were estimated at the same time. A concept of “reduced degree of crystallinity (Rc)” and “critical PEO content” is proposed and applied as a yardstick of the effects of PMMA backbone chains and salts on the crystalline behavior of the PEO graft chains. Xca and Xcg increase with both the content and molecular weight of the PEO graft chains. The critical PEO content, below which PEO crystallinity is not seen, is about 23.7%. PMMA backbone chains can reduce the crystallization of the PEO graft chains at any given PEO content. Xca and Xcg diminish after complexing with the salts and the order of reducing crystallinity is: LiClO4 > KSCN > FeCl₂; salts have two inverse effects, reduction and promotion, on the crystallization of the PEO graft chains. The salt effects depend on the salt concentrations and coordination of the cations. The crystallite sizes in the PEO graft chains are smaller than those in the PEO homopolymers but increase after complexing with salts. The PEO crystallite sizes are not noticeably affected by the content and molecular weight of the PEO graft chains but are noticeably affected by salt concentration.     

Temperature‐Induced Pattern Transition in Crystallizing Ultrathin Polymer Films

The crystallization patterns of ultrathin poly(ethylene oxide)/poly(methyl methacrylate)(PEO/PMMA) blend films crystallized at different undercooling were investigated by atomic force microscopy. Dendrite pattern formed as a result of crystalline anisotropy at low undercooling and evolved into seaweed pattern with increasing undercooling. Although the configuration of macromolecules is far different from that of simple small molecules, the crystallization pattern transition in ultrathin polymer films can be interpreted by the classical morphology diagram developed on the basis of metals and simple molecules, indicating that polymer chains can be considered as simple dynamical units in a quasi‐two‐dimensional confined state.     

Miscibility,Crystallization, and Morphology of the Double-Crystalline Blends of Insulating Polyethylene and Semiconducting Poly(3-Butylthiophene)

A series of crystalline semiconducting poly(3-butylthiophene) (P3BT)/crystalline insulating polyethylene (PE) blends were prepared and the miscibility, crystallization, and structure/morphology were investigated. Even though phase separation was observed by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS), several pieces of evidence indicated that limited miscibility should be present in PE/P3BT blends: small changes in both T_m and crystallinity of PE phase and a small portion of PE being dissolved in P3BT. The study of PE isothermal crystallization kinetics revealed that the introduction of P3BT significantly influenced the nucleation mechanism and growth geometry, i.e., PE was transformed from three-dimensional (3D) spherulitic to two-dimensional (2D) disc crystals. A striking reduction of nucleation density and an obvious ringed morphology of PE spherulites (2D) in PE/P3BT blends were also observed by polarized optical microscopy; it is proposed that the limited miscibility between PE and crystalline P3BT favors the formation of ringed PE spherulite in the blends. Additionally, preferred orientation of PE lamellae, with their b-axis largely constrained to the thin film plane, was observed by X-ray diffraction in PE/P3BT blend films. It is evidenced that the PE orientation was due to the b-axis being the crystal growth direction, which can only be in film plane.     

Solid-state 13C NMR and synchrotron SAXS/WAXS studies of uniaxially-oriented polyethylene

We report solid-state ¹³C NMR and synchrotron wide-and small-angle X-ray scattering experiments (WAXS, SAXS) on metallocene linear low density polyethylene films (e.g., Exceed™ 1018 mLLDPE; nominally 1 MI, 0.918 density ethylene-hexene metallocene copolymer) as a function of uniaxial draw ratio, λ. Combined, these experiments provide an unambiguous, quantitative molecular view of the orientation of both the crystalline and amorphous phases in the samples as a function of draw. Together with previously reported differential scanning calorimetry (DSC), gas transport measurements, transmission electron microscopy (TEM), optical birefringence, small angle X-ray scattering (SAXS) as well as other characterization techniques, this study of the state of orientation in both phases provides insight concerning the development of unusually high barrier properties of the most oriented samples (λ=10). In this work, static (non-spinning) solid-state NMR measurements indicate that in the drawn Exceed^TM films both the crystalline and amorphous regions are highly oriented. In particular, chemical shift data show the amorphous phase is comprised increasingly of so-called “taut tie chains” (or tie chains under any state of tautness) in the mLLDPE with increasing draw ratio – the resonance lines associated with the amorphous phase shift to where the crystalline peaks are observed. In the sample with highest total draw (λ=10), virtually all of the chains in the non-crystalline region have responded and aligned in the machine (draw) direction. Both monoclinic and orthorhombic crystalline peaks are observed in high-resolution, solid-state magic-angle spinning (MAS) NMR measurements of the oriented PE films. The orientation is comparable to that obtained for ultra-high molecular weight HDPE fibers described as “ultra-oriented” in the literature. Furthermore, the presence of a monoclinic peak in cold-drawn samples suggests that there is an appreciable internal stress associated with the LLDPE. The results are confirmed and independently quantified by Herman's Orientation Function values derived from the WAXS measurements. The degree of orientation approaches theoretically perfect alignment of chains along the draw direction. We deduce from this observation that a high fraction of the non-crystalline chains are either tie chains that directly connect adjacent lamellae or are interlocking loops from adjacent lamellae. In either case, the chains are load-bearing and are consistent with the idea of “taut tie chains”. We note that transmission electron micrographs recorded for the ultra-oriented Exceed showed the lamellae are often appreciably thinner and shorter than they are for cast or blown Exceed 1018. Combined with higher crystallinity, the thinner lamellae statistically favor more tie chains. Finally, the remarkably large decrease in permeability of the λ=10 film is primarily attributed to the high degree of orientation (and loss of entropy) of the amorphous phase.     

Influence of Shearing on Crystallization Behavior of Polyoxymethylene/Poly(Ethylene Oxide) Crystalline/Crystalline Blends

The effect of shearing on crystallization behavior of a crystalline/crystalline blend, polyoxymethylene [POM]/poly(ethylene oxide) [PEO], was investigated using polarized light microscopy connected with a CSS450 shearing hot-stage, scanning electron microscopy, differential scanning calorimetry [DSC], and x-ray diffraction [XRD]. The experimental results indicated that the shearing made POM and PEO disperse more evenly and increased the inclusion and entanglement effects between the molecular chains of POM and PEO and therefore enhanced the influence of PEO on the crystallization of POM. As a result, the blend sheared at a shear rate of 20 s^?1 for 10 min at 160°C formed shish–kebab crystals and produced more interlamellar structures compared with the formation of perforated spherulites in the unsheared blend. Moreover, a more obvious shoulder melting peak of POM appeared in the DSC heating trace and a new diffraction peak occurred at 2θ = 31.7° in the XRD pattern for the sheared POM/PEO [50/50] blend.     

Effect of PMMA on crystallization behavior and hydrophilicity of poly(vinylidene fluoride)/poly(methyl methacrylate) blend prepared in semi-dilute solutions

Films of poly(vinylidene fluoride) (PVDF)/poly(methyl methacrylate) (PMMA) blend were derived from a special procedure of casting semi-dilute solutions. Hydrophilic character and crystallization of PVDF were optimized by variation of PMMA concentration in PVDF/PMMA blends. It was found that a PVDF/PMMA blend containing 70 wt% PMMA has a good performance for the potential application of hydrophilic membranes via thermally induced phase separation. The films presented β crystalline phase regardless of PMMA content existed in the blends. Thermal analysis of the blends showed a promotion of crystallization of PVDF with small addition of PMMA which induced larger lamellar thickness of PVDF, leading to the largest spherulitic crystal of PVDF (10 wt% PMMA) is about 8 μm. SEM micrographs illustrated no phase separation occurred in blends, due to the high compatibility between PVDF and PMMA.     

Crystallization Behavior of PEO in Nano‐Structured PEO‐b‐PS/PPO Blends

Blends of poly (ethylene oxide)‐b‐polystyrene (PEO‐b‐PS) diblock copolymer and poly (2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) homopolymer were obtained by solution blending, and the morphologies of PEO dispersed nanoparticles in PPO/PS matrix were observed by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The isothermal crystallization kinetics was studied using differential scanning calorimetry (DSC) and polarized optical microscopy (POM). Nonisothermal crystallization kinetics was studied using DSC. The results showed that PEO segments were easier to crystallize in the blend than in the copolymer probably due to the interfaces of PPO acting as nucleation sites to promote the crystallization of PEO. The crystallization of PEO blocks destroyed the pre‐existing microdomain structure even though the glass transition temperature of the matrix was much higher than the crystallization temperature.     

Disorder-Order-Crystalline State Transitions of PEO-b-PPO-b-PEO Copolymers and their Blends: SAXS/WAXS/DSC Study

The structure in the symmetrical triblock copolymers PEO-b-PPO-b-PEO and their blend with PEO, studied by small angle x-ray scattering (SAXS), wide angle x-ray scattering (WAXS), and differential scanning calorimetry (DSC), pass from melt to the solid state on cooling. On subsequent heating back to the melt, they pass through disordered and ordered molten states, crystalline structure, and finally back to a disordered melt state. At high temperatures these systems are in the melt in the disordered state approximately described by the mean-field theory. The characteristic lengths of these systems, obtained from SAXS, are proportional to R _g . At lower temperatures, their structure changes to a disordered state which can be described by the concentration fluctuation theory. During cooling, the disordered melt structure changes abruptly into the ordered melt structure. The crystallization destroys this melt structure, forming a new lamellar structure with different periodicity. During heating near the melting point, lamellar periodicity increases very steeply. After melting, the crystalline structure transforms directly to the disordered state.     

Study of temperature dependence of crystallisation transitions of a symmetric PEO-PCL diblock copolymer using simultaneous SAXS and WAXS measurements with synchrotron radiation

The reversible transitions of the lamellae of a crystalline-crystalline diblock copolymer from the melt to crystallites were studied using simultaneous small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS) measurements with synchrotron radiation. A symmetric poly(ethylene oxide)-poly( -caprolactone) diblock copolymer was chosen for this study. We showed in the course of the block copolymer crystallisation that the time-resolved integrated intensity I _int was proportional to the product of the volume fractions of the PEO and PCL phases and the scattering contrast due to the electron density difference. These results demonstrated that simultaneous SAXS/WAXS measurements could be used to monitor the crystallisation process in two domains of different sizes at the same time.     

Structure and crystallization of molecular complexes between poly(ethylene oxide) and hydroxybenzenes

The phase diagrams of the binary systems poly(ethylene oxide) (PEO)-resorcinol and poly(ethylene oxide)-p-nitrophenol show the presence of molecular complexes with well-defined stoichiometries. The crystal structure of these two molecular complexes has been determined from wide-angle x-ray diffraction patterns of stretched films and spherulites. The morphology of the two complexes crystallized from the melt is investigated by differential scanning calorimetry and small-angle x-ray scattering. The crystallization of the PEO-resorcinol complex from the melt gives integral-folded crystals with either extended chains (EC) or n-folded chains (n-FC). As observed for PEO oligomers, the fraction of EC crystals of the PEO-resorcinol complex increases with the crystallization temperature to give finally only EC crystals but in a larger range of crystallization temperatures than for pure PEO. On the other hand, the PEO-p-nitrophenol complex crystallizes over all the studied crystallization range as stable nonintegral-folded (NIF) crystals. Two proposals related to the crystal structure of these complexes and their mode of growth are invoked to explain these two greatly different morphologies at the lamellar level.     

Preparation of Poly(vinylidene fluoride)/Poly(methyl methacrylate) Blend Microporous Membranes via the Thermally Induced Phase Separation Process

The thermally induced phase separation (TIPS) process was employed to prepare poly(vinylidene fluoride)/poly(methyl methacrylate) (PVDF/PMMA) blend microporous membranes. The effect of PMMA content on the dynamic crystallization temperature of the PVDF/PMMA/sulfolane system was analyzed. The effects of PMMA weight fraction and cooling rate on the cross-sectional morphology, crystallinity, crystal structure, thermal stability, and porous structure of the resulting membranes were investigated using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and a mercury porosimeter, respectively. The mechanical properties of the membranes were evaluated by tensile tests. It was found that solid–liquid phase separation occurred in the PVDF/PMMA/sulfolane system. Scanning electron microscopy revealed that either increasing PMMA weight fraction or decreasing cooling rate will lead to a macroscopical phase separation between PVDF and PMMA. PMMA weight fraction and cooling rate had some influence on the crystallinity, porous structure, and mechanical properties, but no influence on the polymer crystal structure of the membranes. PMMA weight fraction influenced thermal stability of the final membranes but cooling rate did not.     

Influence of Blend Composition on Crystallization of Poly(L-Lactic Acid)/Poly (Ethylene Oxide) Crystalline/Crystalline Blends

The effect of blend composition on crystallization morphology and behavior of a crystalline/crystalline blend, poly(l-lactic acid) (PLLA)/poly(ethylene oxide) (PEO), during slow, non-isothermal crystallization was studied by polarized light microscopy (PLM) connected with a hot-stage and differential scanning calorimetry (DSC). The results showed that all of the PLLA/PEO blends produced spherulites which gradually became bigger and looser, as well as coarser, with the increment of the PEO content, indicating that the PEO crystals was resided in the interlamellar or interfibrillar (between clusters of commonly oriented lamellae) regions of the PLLA spherulites. In the (25/75) and (10/90) blends, the nucleation and growth processes of the PEO spherulites could be clearly observed in the pre-existing PLLA spherulites. The onset crystallization temperature and the melting point of one component decreased with increasing the content of the other one owing to the good miscibility of the two components in the non-crystalline state and the interaction between their macromolecules, indicating that the crystallization of each component was influenced by the other one.     

Interfacial morphology and friction properties of thin PEO and PEO/PAA blend films

The scanning force microscope (SFM) was used to investigate morphology of poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) blend. The effect of solvent and dewetting in surface structure of PEO film was reported. The results manifested that the crystallization of PEO could be suppressed completely in ultrathin region via using chloroform as a solvent, and the branched-like crystallization was recovered after dewetting. Also, the effect of thickness, the ratio of PEO/PAA and dewetting in surface morphology of PEO-PAA blend films were investigated. These results showed that the crystallization was highly dependent on the ratio of PEO/PAA and the thickness of blend film. Furthermore, we assembled the PEO/PAA layer-by-layer film by spin-casting method for the first time, which exhibited highly efficiency. As a complementary tool, we also used lateral force microscopy (LFM) to explore surface information of these films. The result was indicative of interfacial constraints in ultrathin region, and also was supported by the results showing the spin-casting PEO/PAA blends rather than heterogeneous mixture.     

Investigation of the Melt‐Crystallization of Polypropylene by a Temperature Slope Method

Abstract

To investigate the in‐situ ordering process of isotactic polypropylene (iPP) from a melt state, a stationary growth front was prepared by the temperature slope crystallization (TSC) method. During the melt‐crystallization, iPP was crystallized into the α‐phase or β‐phase depending on the crystallizing conditions. The mechanism of the melt‐crystallization at the growth front was precisely observed by wide‐angle and small‐angle x‐ray scattering (WAXS and SAXS) using a strong synchrotron beam. In the TSC apparatus, the sample was crystallized in between a heater, controlled to 220°C, and a cooler, cooled by water to 25°C. We define the z‐axis parallel to the temperature gradient. A‐lamellae and B‐lamellae are also defined as those whose lamellar normal are perpendicular and parallel to the z‐axis, respectively. In a sample‐stop (SS) stage before the TSC, the original α‐phase lamellae became thicker, approaching to the melt‐solid boundary by annealing. The annealing process showed that the α‐phase B‐lamellae remained and the SAXS reflection was stronger on the meridian near the melt‐solid boundary in the SS stage. In the beginning of the TSC, the α‐phase B‐lamellae developed as a primary crystallization. During secondary crystallization under high supercooling, the SAXS cross pattern appeared showing that the α‐phase developed both A‐ and B‐lamellae. As the growth direction of A‐lamellae is parallel to the z‐axis, A‐lamellae grow faster than B‐lamellae. By the self‐epitaxial mechanism on the side surface of the A‐lamellae, the B‐lamellae grow on the base of the A‐lamellae. Following appearance of a spontaneous β‐nucleus, the β‐phase lamellae grew preferentially, excluding the α‐phase, and occupied the whole area of the sample. In this case also, A‐lamellae are advantageous to grow because of the growth direction parallel to the z‐axis. As a result, the SAXS β‐phase reflection appeared on the equator.     

Onset of tethered chain overcrowding

We proposed an approach to precisely control the density of tethered chains on solid substrates using PEO-b-PS and PLLA-b-PS. As the crystallization temperature Tx increased, the PEO or PLLA lamellar crystal thickness d(L) increased as well as the reduced tethering density sigma; of the PS chains. The onset of tethered PS chains overcrowding in solution occurs at sigma(*) approximately 3.7-3.8 as evidenced by an abrupt change in the slope between (d(L))(-1) and Tx. This results from the extra surface free energy created by the tethered chain that starts to affect the growth barrier of the crystalline blocks.     

Crystallization in Microdomains of a Block Copolymer Comprising Semicrystalline Block Observed by Simultaneous Measurement of SAXS and WAXS with H v‐SALS or DSC

Abstract

Semicrystalline block copolymers provide us with a fascinating model for studying the kinetics of crystallization. We performed the simultaneous measurement of small‐ (SAXS) and wide‐angle (WAXS) x‐ray scattering (SWAXS) with differential scanning calorimetry (DSC), or SWAXS with small‐angle light scattering (H _v‐SALS). The specimen used was polyethylene‐b‐poly(ethylene propylene) (PE‐b‐PEP) with the molecular weight of 44,200. The PE block has the melting point (T _m) at 108°C. We observed the time evolution of crystallization in the lamellar microdomains of PE‐b‐PEP after a temperature drop from 180°C (?T _m) to a variety of temperatures slightly below T _m. The exothermic signal was observed by DSC right after the temperature drop, while the four‐leaf‐clover pattern of H _v‐SALS and the SAXS peaks due to the lamellar microdomains were observed several minutes after the temperature equilibration. The WAXS peaks of (110) and (200) reflection were almost simultaneously detected with the H _v‐SALS and the SAXS peaks at crystallization temperature of 100°C. With the crystallization temperature closer to T _m, the WAXS crystalline signals showed up with longer time lag after the H _v‐SALS and the SAXS peaks began to appear. Interestingly, these phenomena are interpreted as that long‐range order of density fluctuation up to the order of micrometers was generated prior to the formation of crystals with partially ordered phase rather than the instantaneous crystalline nucleation.     

A novel PEO-based blends solid polymer electrolytes doping liquid crystalline ionomers

A novel PEO-based blends solid polymer electrolytes doping liquid crystalline ionomers (LCI), PEO/PMMA/LiClO₄/LCI, and PEO/LiClO₄/LCI were prepared by solution casting technology. Scanning electron microscope (SEM) and energy-dispersive spectroscopy (EDS) analysis proved that LCI uniformly dispersed into the solid electrolytes and restrained phase separation of PEO and PMMA. Differential scanning calorimetry (DSC) results showed that LCI decreases the crystallinity of blends solid polymer electrolytes. Thermogravimetric analysis (TGA) proved LCI not only improved thermal stability of PEO/PMMA/LiClO₄ blends but also prevent PEO/PMMA from phase separation. Infrared spectra results illustrated that there exists interaction among Li⁺ and O, and LCI that promotes the synergistic effects between PEO and PMMA. The EIS result revealed that the conductivity of the electrolytes increases with LiClO₄ concentration in PEO/PMMA blends, but it increases at first and reaches maximum value of 2.53?×?10^?4 S/cm at 1.0 % of LCI. The addition of 1.0 % LCI increases the conductivity of the electrolytes due to that LCl promoting compatibility and interaction of PEO and PMMA. Under the combined action of rigidity induced crystal unit, soft segment and the terminal ionic groups in LCI, PEO/PMMA interfacial interaction are improved, the reduction of crystallinity degree of PEO leads Li⁺ migration more freely.     

Kinetics of Isothermal and Nonisothermal Crystallization of Poly(ethylene oxide) (PEO) in PEO/Fatty Acid Blends

In this work, isothermal and nonisothermal crystallization kinetics of poly(ethylene oxide) (PEO) and PEO in PEO/fatty acid (lauric and stearic acid) blends, that are used as thermal energy storage materials, was studied using differential scanning calorimetry (DSC) data. The Avrami equation was adopted to describe isothermal crystallization of PEO and nonisothermal crystallization was analyzed using both the modified Avrami approach and Ozawa method. Avrami exponent (n) for PEO crystallization was in the range 1.08–1.32 (10–90% relative crystallinity), despite of spherulites formation, while for PEO in PEO/fatty acid blends n was between 1.61 and 2.13. Hoffman and Lauritzen theory was applied to calculate the activation energy of nucleation (K_g) – the lowest value of K_g was observed for pure PEO, despite of heterogeneous nucleation of fatty acid crystals in PEO/fatty acid blends. For nonisothermal crystallization of PEO in PEO/lauric acid (1:1 w/w) and PEO/stearic acid (1:3 w/w) blends, secondary crystallization occurred and values of the Avrami exponent were 2.8 and 2.0, respectively. The crystallization activation energies of PEO were determined to be ?260 kJ/mol for pure PEO, ?538 kJ/mol for PEO/lauric acid blend, and ?387 kJ/mol for PEO/stearic acid blend for isothermal crystallization and ?135,6 kJ/mol, ?114,5 kJ/mol, and ?92,8 kJ/mol, respectively, for nonisothermal crystallization.     

Phase separation and nanocrystallization in Al92Sm8 metallic glass

Crystallization of Al₉₂Sm₈ metallic glass was investigated in situ using combined small-angle and wide-angle X-ray scattering (SAXS/WAXS) techniques during isothermal annealing at temperatures close to crystallization point. A continuously growing interference maximum shifting progressively towards lower angles was found to develop in SAXS regime. Simultaneously taken WAXS spectra reveal formation of fcc-Al nanocrystalline phase. The analysis of the SAXS/WAXS data indicate that amorphous phase separation is responsible for the nanocrystalline microstructure formation. The primary fcc-Al crystals nucleate inside the Al-rich amorphous regions formed during alloy decomposition and their growth is constrained by the region size.