Finite size effects in multilayered polymer systems: Development of PET lamellae under physical confinement

The glass transition temperature and the crystallization behaviour of poly(ethylene terephthalate) PET ultra-thin layers (a few tens of nm) within multilayered PET/polycarbonate (PC) coextruded films are investigated as a function of layer thickness by means of calorimetric measurements. Results are discussed in terms of reduced thickness and interface effects. The appearance and evolution of lamellar orientation upon isothermal crystallization of ultra-thin PET layers from the glassy state are explored based on real time small-angle X-ray scattering (SAXS) studies. Analysis of the SAXS measurements reveals that finite size effects hamper the crystallization process. However, the final lamellar structure is similar in both, the nanolayered PET and the bulk material. Results suggest that not only lamellar insertion but also some lamellar thickening contribute to the development of the final lamellar structure. Room temperature SAXS and wide-angle X-ray diffraction (WAXS) measurements indicate that two lamellar populations develop: edge-on lamellae are proposed to appear close to the interphases while flat-on lamellae, arising as a consequence of confinement, should be preferentially located in the layers core.     

Dynamic interplay between phase separation and crystallization in a poly(?-caprolactone)/poly(ethylene glycol) oligomer blend

We have investigated the crystallization effect on the phase separation of a poly(?-caprolactone) and poly(ethylene glycol) oligomer (PCL/PEGo) blending system using simultaneous small-angle light scattering and differential scanning calorimetry (SALS/DSC) as well as simultaneous small-angle X-ray scattering (SAXS), wide-angle X-ray scattering (WAXS), and DSC (SAXS/WAXS/DSC). When the PCL/PEGo system, of a weight ratio of 7/3, is quenched from a melt state (160 °C) to temperatures below the spinodal point and the melting temperature of PCL (63 °C), the structural evolution observed exhibits characteristics of (I) early stage of spinodal decomposition (SD), (II) transient pinning, (III) crystallization-induced depinning, and (IV) diffusion-limited crystallization. The time-dependent scattering data of SALS, SAXS and WAXS, covering a wide range of length scale, clearly show that the crystallization of PCL intervenes significantly in the ongoing viscoelastic phase separation of the system, only after the early stage of SD. The effect of preordering before crystallization revives the structural evolution pinned by the viscoelastic phase separation. The growth of SAXS intensity during the preordering period conforms to the Cahn-Hilliard theory. In the later stage of the phase separation, the PCL-rich matrix, of spherulite crystalline domains developed due to the faster crystallization kinetics, traps the isolated PEGo-rich domains of a slower viscoelastic separation.     

Shear-induced crystallization of isotactic polypropylene within the oriented scaffold of noncrystalline ultrahigh molecular weight polyethylene

Shear-induced crystallization of isotactic polypropylene (iPP) within the oriented scaffolds of noncrystalline ultrahigh molecular weight polyethylene (UHMWPE) was investigated by means of in situ synchrotron small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD). The study was carried out using iPP/UHMWPE blends under isothermal crystallization at 145 °C (i.e., above the melting point of polyethylene) and step shear (shear rate=60 s⁻¹, duration=5 s) conditions. The oriented and isotropic iPP crystalline phases were extracted from the 2D WAXD pattern, and their kinetics data were evaluated with the Avrami equation. The dominant component in the oriented iPP phase was a kebab structure, whose nanostructure dimensions were determined by a novel SAXS analysis scheme. The minor non-crystalline but oriented UHMWPE component played a key role in the nucleation of iPP, which could be explained in terms of mutual diffusion at the interface, resulting in a significant increase in the relaxation time of iPP chains. As a result, after shear, the interfacial iPP chains could also retain their orientation and formed oriented nuclei to initiate the kebab growth.     

A Raman Spectroscopic Study of Phase Transformations in Titanium-Containing Magnesium Aluminosilicate Glasses

The evolution of the Raman spectra of the 20MgO · 20Al₂O₃ · 60SiO₂ glass with 10 mol % TiO₂ and glasses doped with 0.5 wt % NiO or 2.5 and 5.0 mol % Ga₂O₃ is investigated in the course of heat treatment resulting in phase separation and crystallization. The composition and structure of the amorphous and crystalline phases (precipitating in the course of phase separation) and the residual glass are analyzed on the basis of Raman scattering, small-angle X-ray scattering (SAXS), and X-ray powder diffraction data. The size of nanoparticles of the precipitated phases is determined by low-frequency Raman spectroscopy, and the results obtained are compared with the nanoparticle size derived from the SAXS data.     

Crystallization Study of Glassy PET/PEN Blends by Means of Real Time X-ray Scattering

Abstract

The crystallization of several blends of poly(ethylene terephthalate) (PET) and poly(ethylene 2,6 naphthalene dicarboxylate) (PEN) has been investigated by wide angle- (WAXS) and small angle X-ray scattering (SAXS) using synchrotron radiation. The role of transesterification reactions, giving rise to a fully amorphous non-crystal-lizable material (copolyester) is brought up. For the blends rich in PET, crystallization temperatures (T_c ) of 105 and 117°C were used. For blends rich in PEN, crystaffization was performed at T_c =150 and 165°C, respectively. The time variation of the degree of crystallinity was fitted into an Avrami equation considering the induction time prior to the beginning of crystallization. The Avrami parameters, the half times of crystallization, as well as the nanostructure development (SAXS invariant and long period) for the blends, are discussed in relation to blend composition and are compared to the parameters observed for the homopolymers PET and PEN.     

Confined crystallization in end-linked PEO network under uniaxial extension

In this work extension induced crystallization of end-linked polyethylene oxide (PEO) network was investigated with in-situ small angle X-ray scattering (SAXS) and rheological measurement. The coupling between crystallinity and stress of crosslinked network makes the morphology time dependent. With a large strain the structure evolution in the stretched network is found to follow a two-stage process: i) crystals with high numerical density and small dimension form first, which laterally correlate with adjacent ones; ii) continuous melting and fusing of adjacent crystal happen after the first nucleation stage, leading to increase of crystal dimension and stability. Decreasing strain a gradual transformation to normal lamellae formation is found. Strain tuned confinement and crystallization induced confinement release is supposed to induce the structural change.     

Nanostructure evolution of oriented high-pressure injection-molded poly(ethylene) during heating

High-pressure injection-molded polyethylene (PE) rods are studied by ultra small-angle X-ray scattering from synchrotron during the heating of the polymer. Injection of a cool melt into a cold mold yields highly oriented PE rods with a core-shell structure. Samples from both the core and the shell material are studied. The two-dimensional scattering patterns are evaluated utilizing the multi-dimensional chord distribution function (CDF) analysis. From the obvious evolution of the nanostructure during successive crystallite melting, the sequence of processes occurring during crystallization is elucidated. First, nuclei form one-dimensional lattices with short-range order along the fiber axis. From this row structure, lamellae grow with wide lateral extension. An indication of an intermediate block structure is observed. Finally two steps of insertion crystallization result in two long period halvings. Increase of the mold pressure increases the lateral extension of the inserted lamellae in the shell material. In the core material a uniform row structure is absent. Extended primary lamellae form stacks with decreasing long periods before insertion crystallization takes over. But crystallites inserted in the core material do not form extended lamellae. Each of these steps leaves its footprint in the nanostructure and the corresponding scattering pattern. After CDF interpretation of the heating series, the room temperature pattern can be explained. The strong two-point pattern is associated with the primary lamellae and the intensity ridge extending along the meridian results from irregular insertion of lamellae. When the row structure is observed in the CDF, the fiber pattern exhibits equatorial scattering.Domain roughness generates a strong background scattering, which cannot be separated in one step. For the presented material it is shown that iterative background subtraction eliminates the scattering effects of the imperfect (i.e. inserted) lamellae.     

Structural changes in isothermal crystallization process of polyoxymethylene investigated by time-resolved FTIR, SAXS and WAXS measurements

Structural evolution in the isothermal crystallization process of polyoxymethylene from the molten state has been investigated by carrying out the time-resolved measurements of infrared spectra and synchrotron small angle X-ray scattering (SAXS) and wide angle X-ray scattering. In case of isothermal crystallization at 130 °C, for example, the infrared bands intrinsic of folded chain crystal (FCC) morphology appeared at first, and then the bands of extended chain crystal (ECC) morphology were detected with time delay of ca. 150 s. In the SAXS experiment at 130 °C, the lamellar stacking structure of the long period of ca. 15 nm was observed at first, which changed rapidly to ca. 12 nm in a short time. The SAXS peak with the long period of ca. 6 nm started to appear with a time delay of ca. 150 s after the initial lamellae appeared and coexisted with the initially-observed 12 nm peak. Judging from the timing to detect these characteristic infrared and SAXS signals, a good correspondence was found to exist between the stacked lamellar structure of 12 nm long period and FCC morphology and between the structure of 6 nm long period and ECC morphology. The quantitative analysis was made for the SAXS data on the basis of the lamellar insertion model combined with the paracrystalline theory of the second-kind of disorder. The following structural evolution was deduced from all these results. Immediately after the temperature jump from the melt to 130 °C, the stacked lamellar structure of FCC morphology was generated at first. New lamellae were formed from the amorphous region in between the originally-existing lamellae about 150 s later, where the random chain segments bridging the adjacent lamellae were extended to form the taut tie chains, giving infrared bands of ECC morphology. This inserted lamellar structure of 6 nm long period coexisted at a population of ca. 6% with the initially-formed lamellar stacking structure of 12 nm long period. When the experiment was made at 150 °C, only the formation of stacked lamellar structure of FCC morphology was observed and the insertion of new lamella did not occur.     

On the fractal character of polymer spherulites: an ultra‐small‐angle X‐ray scattering study of poly[(R)‐3‐hydroxybutyrate]

Ultra‐small‐angle X‐ray scattering (USAXS) and small‐angle X‐ray scattering (SAXS) measurements are presented for poly[(R)‐3‐hydroxybutyrate] (PHB) crystallized at room temperature. The USAXS patterns indicated that the spherulites had a radially orientated fibrillar nanostructure with fractal geometry over a length scale ranging from 12 nm up to at least 300 nm, with a mass fractal dimension of approximately 2.7 in aged samples. The SAXS patterns indicated that the fibrils themselves were built up of bundles of crystalline lamellae separated by layers of disordered material, with a period length of approximately 6 nm. The SAXS measurements during primary crystallization gave an initial fractal dimension of 4 during spherulite growth, due to the sharp phase boundary between the spherulites and the melt. Copyright © 2004 Society of Chemical Industry     

Micro-phase separation and crystallization behavior of amorphous oriented PLLA/PVAc blends during heat treatment under strain

Amorphous oriented poly(l-lactide) (PLLA)/poly(vinyl acetate) (PVAc) 50/50 films were prepared by uniaxial drawing of melt-mixed blends at 65 °C. The morphology development and crystal organization of the blends during heat treatment under strain were investigated using small angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD). Equatorial scattering maxima in the SAXS patterns for samples annealed at 75 °C were observed before the appearance of crystal reflections. Further annealing of the samples at higher temperature induced two further discrete meridian scattering maxima. The observations indicated that homogenous oriented PLLA/PVAc film undergoes micro-phase separation first, followed by crystallization of PLLA in the PLLA-rich phase. The micro-phase separated PVAc nanodomains are aligned parallel to the stretching direction, whereas the crystallized PLLA lamellae are oriented perpendicular to the stretching direction (crystal c-axis along the stretching direction). Micro-phase separation was not observed when films were annealed at 120 °C, at which temperature the high crystallization rate of PLLA overwhelmed the micro-phase separation process.     

Isothermal crystallization of poly(glycolic acid-alt-6-hydroxyhexanoic acid) studied by DSC and real time synchrotron SAXS/WAXD

The thermal properties and the isothermal hot crystallization behavior of a new regular polyester constituted of glycolic acid and 6-hydroxyhexanoic acid units were studied by differential scanning calorimetry (DSC). The morphological development during isothermal crystallization was also investigated using simultaneous small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) techniques with synchrotron radiation. A crystalline-amorphous two-phase lamellar system was assumed and interpreted using correlation functions.Kinetic parameters deduced from the Avrami analysis indicated a three-dimensional spherulitic growth from heterogeneous nuclei, whereas optical micrographs revealed the formation of small spherulites with a negative birefringence and a fibrillar texture. The Lauritzen and Hoffman analysis of crystallization regimes was performed taking into account the kinetic constants of the overall crystallization process deduced from DSC and also the reciprocal crystallization halftimes evaluated by means of DSC, SAXS and WAXD experiments. Data were consistent with a single crystallization regime and yielded similar values for the transport activation energy and the nucleation constant in all cases.The evolution of long period and lamellar thickness was evaluated during crystallization. Changes with both crystallization time and crystallization temperature were significant.     

Structural evolution of tensile deformed high-density polyethylene at elevated temperatures: Scanning synchrotron small- and wide-angle X-ray scattering studies

The structural evolution of an ice-quenched high-density polyethylene (HDPE) subjected to uniaxial tensile deformation at elevated temperatures was examined as a function of the imposed strains by means of combined synchrotron small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS) techniques. The data show that when stretching an isotropic sample with the spherulitic structure, intralamellar slipping of crystalline blocks was activated at small deformations, followed by a stress-induced fragmentation and recrystallization process yielding lamellar crystallites with their normal parallel to the stretching direction. Stretching of an isothermally crystallized HDPE sample at 120 °C exhibited changes of the SAXS diagram with strain similar to that observed for quenched HDPE elongated at room temperature, implying that the thermal stability of the crystal blocks composing the lamellae is only dependent on the crystallization temperature. The strain at a characteristic transition point associated with the first indication for the occurrence of a fibrillar structure remains essentially constant in spite of the large changes in drawing temperature and crystalline thickness. In addition, WAXS experiments were used to probe the texture changes accompanying the uniaxial elongation and yield the relationship between the orientational order parameters associated with the crystallites and the amorphous chain segments, and the imposed strain. The results support the existence of intralamellar slip processes from the very beginning of tensile deformation.     

Combined effect of shear and fibrous fillers on orientation-induced crystallization in discontinuous aramid fiber/isotactic polypropylene composites

The shear-induced crystallization behavior in isotactic polypropylene (iPP) composite melt containing short aramid fibers was investigated by means of WAXD (wide-angle X-ray diffraction) and SAXS (small-angle X-ray scattering) techniques using synchrotron radiation. The study was carried out in a post-shear isothermal crystallization mode at temperatures of 140-160 °C. Parameters pertaining to the crystallization morphology and kinetics were analyzed, including total crystallinity, orientated crystalline and amorphous fractions, dimensions of the formed shish-kebab structure, as well as induction time and rate of crystallization. The individual contributions of shear and fibers were evaluated and the combined effect was compared. The results clearly indicated that the effect is synergistic rather than additive.     

Insights into the formation of microporous materials by in situ X-ray scattering techniques

Here we demonstrate the power of in situ scattering techniques in the understanding of formation of nanoporous aluminosilicate and aluminophosphate materials. We utilised a number of X-ray techniques, in particular, in situ energy dispersive X-ray diffraction (EDXRD) and small angle and wide angle X-ray scattering (SAXS/WAXS) techniques for this purpose. The in situ SAXS measurements show the formation of homogeneous precursors in the size of ca. 10 nm, prior to the crystallization of LTA. The crystal size is estimated by fitting the SAXS patterns with an equation for a cubic particle, and it is revealed that the final crystal size of the LTA depends on the synthesis temperature. Whereas, the crystallisation of CoAlPO-5, occurs through the formation of poly-dispersed particles with an average size of the precursor particle of ca. 50 nm. Also shown the effect of temperature and structure directing organic cations on the production of CoAlPO-5 materials.     

A small angle X-ray scattering and electrochemical study of the decomposition of wood during pyrolysis

The pyrolysis of nine wood samples (Basswood, Cherry, Pine, Walnut, Maple, Hickory, Paduak, Tigerwood and Ipe) between 30 and 1200 °C was investigated. Using Small angle X-ray scattering (SAXS), the thermal degradation of the cellular structure of wood followed by the onset and growth of graphene sheets and associated nanoporosity between the sheets, was observed as temperature increased. SAXS, wide angle X-ray scattering and electrochemical studies of Na insertion using Na batteries were used to study the wood samples pyrolyzed to 1100 °C. Regardless of the original wood precursor used during pyrolysis, the nanostructure and resulting electrochemical behaviour of all the wood samples were similar after heating to 1100 °C.     

超拉伸UHMWPE纤维的结晶结构及其形成机理

采用冻胶纺丝-超拉伸技术纺制了超高相对分子质量聚乙烯(UHMWPE)纤维。利用小角X光散射(SAXS)、广角X射线衍射(WAXD)及拉曼光谱等测试手段,研究了拉伸过程中UHMWPE纤维的结晶结构变化。结果表明:随拉伸的进行,纤维非晶区中分子链逐渐参与了结晶,纤维SAXS强度减弱,纤维结构变得紧密规整;纤维结晶长周期及结晶度随拉伸倍数的增加而增大,并趋于平衡,拉伸30倍后,纤维结晶长周期约为50 nm,结晶度约为67.5％;纤维横向晶粒平均尺寸随拉伸倍数的增加而变小,拉伸30倍后,趋于平衡,而纤维晶粒c轴方向的轴向晶粒尺寸随拉伸倍数的增加而变大。     

Double liquid crystalline side-chain type block copolymers for hierarchically ordered nanostructures: Synthesis and morphologies in the bulk and thin film

Well-defined double liquid crystalline side-chain type block copolymers (DLC-BCPs) were synthesized by nitroxide-mediated living free radical polymerization (NMP) of two different types of styrene monomers containing liquid crystalline moieties. The molecular weights and compositions were controlled by changing the polymerization time and/or the feed amount of the monomers. The bulk morphologies were studied using wide-angle X-ray scattering (WAXS), small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). DLC-BCPs were favored to form microphase-separated lamellar structures over a wide range of volume fractions. By controlling the annealing conditions, further higher-ordered hierarchical nanostructures were obtained with a long-range alignment, in which the semi-crystalline side-chains were oriented parallel to the interface of microphase-separated lamellar structure. Thin film morphology was investigated using atomic force micrography (AFM). The formation of lamellar nanostructure with a long-range alignment vertically oriented to the silicon wafer substrate was achieved by simple thermal annealing.     

Structural and morphological development in poly(ethylene-co-hexene) and poly(ethylene-co-butylene) blends due to the competition between liquid-liquid phase separation and crystallization

Isothermal crystallization behavior of poly(ethylene-co-hexene) (PEH) and the 50/50 blend (H50) of PEH with amorphous poly(ethylene-co-butylene) (PEB) was studied by time-resolved synchrotron simultaneous small-angle X-ray scattering/wide-angle X-ray diffraction (SAXS/WAXD) techniques and optical microscopy (OM). The X-ray study revealed the changes of structural and morphological variables such as the scattering invariant, crystallinity and lamellar long period, et al. In H50, the lamellar morphology was found to be dependent on competition between liquid-liquid phase separation (LLPS) and crystallization. At high temperature, LLPS becomes dominating, resulted in crystallization of PEH with minimal influence of PEB. At low temperature, LLPS is suppressed, PEB component shows obvious influence on PEH crystallization, PEB is thought to be partially included into PEH lamellar stacks and PEH-PEB co-crystallization is unlikely, however, possible. Optical microscopy was used to monitor crystal nucleation and growth rates in PEH and H50, providing complementary information about the effect of temperature on LLPS and crystallization. Real-space lamellar morphologies in PEH and H50 were characterized by atomic force microscopy (AFM), PEH exhibited sheaf-like spherulites while H50 exhibited hedrites. Overall, the competition between LLPS and crystallization in H50 blend influences the structural and morphological development. Controlling the interplay between LLPS and crystallization of PEH/PEB blends, it is possible to control the structure and morphology as practically needed.     

Structure and orientation development in biaxial stretching of ultrahigh molecular weight polyethylene gel films

Ultrahigh molecular weight polyethylene (UHMWPE) gel films were prepared by gelation crystallization from decalin solutions. According to wide- and small-angle X-ray scattering (WAXD and SAXS) studies, single crystal mat texture with crystal c-axis oriented normal to film surface generally develops. However, randomly oriented structure can also develop if an external force is applied to gel films during gelation crystallization. Both textures invariably yield high drawability in uniaxial mode with outstanding modulus and strength. Biaxial films, typically 5 × 5, 6 × 6, 8 × 8, and 10 × 10 times the original dimensions, were prepared at 130°C–135°C in a biaxial stretcher. Optical microscopic Investigations reveal the development of interwoven fibrillar structure in all specimens. WAXD and SAXS studies show that lamellar structure transforms to fibrillar texture during biaxial stretching. Crystal orientation is characterized by WAXD pole figure and infrared dichroic methods. Mechanical studies suggest that tensile modulus and strength appear uniform. In comparison with uniaxial deformation, significant improvement in the lateral strength is seen in the biaxially stretched films.     

Structural modifications in stretch-induced crystallization in PVDF films as measured by small-angle X-ray scattering

The nanostructure of stretched and nonstretched PVDF samples was studied by small-angle X-ray scattering (SAXS). The crystallinity of the samples was determined by wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC), and crystalline phases by Fourier transform infrared spectroscopy (FTIR). The nanostructure can be described by a lamellar stacking of crystalline and amorphous layers, with a fairly well defined long period D and a diffuse-boundary in the interface between the crystalline and amorphous phases. The crystallinity of the stretched sample was found to be greater than that of the nonstretched sample. The long period D and the thicknesses of the crystalline lamellae T_c were found to be greater in the stretched sample than those in the nonstretched sample. The thickness of the diffuse-boundary was evaluated as being ∼ 1.4 nm in the nonstretched sample and 1.1 nm in the stretched sample. It was concluded that the growth of the thickness of the crystalline layer induced by the stretching process (stretch-induced crystallization) occurs partially at expense of the diffuse boundary and also by the coarsening of the structure with the stretching process, because of the diminution in the surface area to volume ratio observed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012