Spatial distribution of lamella structure in PCL/PVB band spherulite investigated with microbeam small- and wide-angle X-ray scattering

The microbeam small- and wide-angle X-ray scattering (SAXS/WAXS) technique gives the novel information about micron-scale structural inhomogeneity of polymer crystal. By using this technique, we have studied structural inhomogeneity of lamella within the band spherulite of miscible polymer blend poly(ε caprolactone) (PCL)/poly(vinyl butyral) (PVB) and the structure development of lamella during crystallization. It is known that PCL/PVB forms very large spherulites (∼several mm in radius) with highly regular band structure because of low frequency of nucleation and that PCL/PVB crystallized at 41 °C has at least two kinds of lamella structure (150 Å, 180 Å). With an X-ray microbeam initially fixed outside near the growth front of the band spherulite, we have observed the lamella formation at the local point and have found that the larger long period grows before the appearance of the shorter long period. We have also observed that the orientation of lamella with the larger long period is different from that of lamella with the shorter long period from SAXS experiment with an X-ray microbeam scanning the band spherulite along its radial direction. Further, the discontinuity in lamella twisting was observed from scanning microbeam WAXS. Based on the experimental results, we propose two possible spatial distribution models. The result of PCL/PVB crystallized at 35 °C was also discussed.     

Deformation behavior of banded spherulite during drawing investigated by simultaneous microbeam SAXS-WAXS and POM measurement

The local deformation behavior inside a poly(ε caprolacton) (PCL)/polyvinylbutyral (PVB) banded spherulite during drawing was observed by in-situ microbeam small-angle X-ray scattering (SAXS) - wide-angle X-ray scattering (WAXS) - polarized optical microscopy (POM) simultaneous measurements. From experimental results, we found that the local deformation of a PCL/PVB banded spherulite can be divided into four stages. In stage I, disordering of the crystalline structure occurs. In stage II, the disordering of the crystalline structure ceases and disordering of the stacking and coarse slippage of the lamellae occur. In stage III, after the breakdown of the twisted lamella structure, the reconstruction of a long period structure occurs. In stage IV, further lamella slippage occurs. Our results show no evidence of fine slippage at a local region during the drastic decrease in the long period. This strongly indicates that the melting and recrystallization mechanism occurs during the lamella reconstruction of PCL/PVB.     

Lamellar morphology of high molecular weight poly(ether ether ketone) after rolltrusion

A rolltrusion technique has been applied to impose high molecule orientation in unreinforced poly(ether ether ketone). The relationships among processing, microstructure and properties were characterized. The morphology was controlled and investigated in the microstructural levels of crystallinity, chain orientation, lamellae and spherulite colony. The density measurements detected an increase in crystallinity after rolltrusion. Wide-angle X-ray scattering (WAXS) diffraction experiments showed the preferred c-axis chain orientation along the rolltrusion direction. The internal microstructure, revealed by permanganic etching and scanning electron microscopy (SEM), changed from randomly distributed lamellae to a row structure. The lamella thickness was estimated to be about 100 Å.     

Penetration of PBSU spherulite into P(VDC-VC) spherulite observed with microbeam- and macrobeam-SAXS/WAXS measurements

PBSU/P(VDC-VC) is a crystalline/crystalline miscible polymer blend, which has characteristics that (1) the melting temperature difference is small (ΔT=33 °C), (2) the spherulite of both components can be observed with polarized optical microscope (POM), and (3) the interpenetrated spherulite is formed under specific condition: Interpenetrated spherulite means a structure formed by the penetration of PBSU spherulite growing into P(VDC-VC) spherulite. In order to clarify the nano-structure of penetrated P(VDC-VC) spherulite and penetrating PBSU lamella, we have performed the microbeam (beam size: about 10×10 μm²) SAXS/WAXS simultaneous measurements as well as macrobeam SAXS/WAXS during formation of the interpenetrated spherulite. From our experimental results, we have concluded that P(VDC-VC) lamellae hardly stack and isolate from each other, and that PBSU penetrates into the inter-fibril region of P(VDC-VC) spherulite. Further, it is found that PBSU lamella penetrating into P(VDC-VC) spherulite excludes amorphous P(VDC-VC) from PBSU inter-lamella region.     

Morphology and electrical properties of carbon black-filled poly(ε-caprolactone)/poly(vinyl butyral) blends

Electrical properties of poly(ε-caprolactone) (PCL)/poly(vinyl butyral) (PVB) blends containing carbon black (CB) were studied as a function of a small amount of PVB content and a wide range of molecular weight of PVB. For samples with the same CB content, the intensity of positive temperature coefficient (I_PTC, defined as the ratio of peak resistivity to resistivity at room temperature) of the blends was increased, with PVB content greatly and molecular weight of PVB weakly. As the band spacings of PCL spherulites in PCL/PVB blends decrease with PVB content and molecular weight of PVB, the changes of the positive temperature coefficient property are ascribed to the morphological difference (i.e., period of twisted lamellae) in the blends. We confirmed our previous conclusion that the origin of the positive temperature coefficient phenomenon is the changes of the distribution of the CB on the melting of the crystalline phase. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 193–199, 1998     

Conductive-filler-filled poly(ϵ-caprolactone)/poly(vinyl butyral) blends. I. Crystallization behavior and morphology

The crystallization behavior and morphology of poly(ϵ-caprolactone) (PCL)/poly(vinyl butyral) (PVB) blends containing carbon black (CB) were studied as functions of PVB and CB content. The presence of CB had no influence on the primary nucleation of PCL crystals or the spherulitic growth rate. They were only influenced by the blend ratio of PVB. The growth rates of spherulites were unchanged throughout the crystallization process, regardless of the CB content. The results indicate that the concentration of PCL at the front of growing spherulite remains constant during crystallization. The distribution of CB in the spherulites was observed using atomic force microscopy to explain these results. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 797–802, 1997     

Crystallization and thermoelectric behavior of conductive-filler-filled poly(ε-caprolactone)/poly(vinyl butyral)/montmorillonite nanocomposites

Crystallization and thermoelectric properties of poly(ε-caprolactone) (PCL)/poly(vinyl butyral) (PVB)/montmorillonite (MMT) nanocomposites containing carbon black (CB) have been studied as a functions of a small amount of amorphous PVB content and a wide range of molecular weight of PVB. X-ray diffraction data of PCL/PVB/MMT nanocomposites indicates most of the swellable silicate layers are exfoliated and randomly dispersed into PCL/PVB system. The band spacings of PCL spherulites in PCL/PVB/MMT nanocomposites decrease with increasing PVB content, and this indicates that increasing the PVB content greatly shortens the period of lamellar twisting. The presence of 1 wt% MMT and higher molecular weight of PVB also shorten the period of PCL lamellar twisting. Nucleation and crystallization parameters, such as growth rate G and Avrami exponent n, can be determined by using POM and DSC isothermally crystallized at 41 °C. For samples with the same CB content, the intensity of positive temperature coefficient (PTC) (I_PTC, defined as the ratio of peak resistivity to resistivity at room temperature) of the nanocomposites was increased as the content and the molecular weight of PVB increases. The change of the PTC property related to the morphological difference (i.e. period of lamellar twisting) in the nanocomposites can be discussed.     

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.     

Morphology and electrical properties of carbon‐black‐filled poly(ϵ‐caprolactone)/poly(vinyl butyral) nanocomposites

The morphology of poly(ε‐caprolactone) (PCL)/poly(vinyl butyral) (PVB)/clay nanocomposites was studied as a function of a small amount of amorphous PVB by polarized optical microscopy. The band spacings of PCL spherulites in PCL/PVB/clay nanocomposites decreased with increasing PVB content, and this indicated that increasing the PVB content shortened the period of lamellar twisting. The electrical properties of PCL/PVB/clay nanocomposites containing carbon black (CB) were also measured as a function of the PVB content. For samples with the same CB content, the intensity of the positive temperature coefficient (defined as the ratio of the peak resistivity to the resistivity at room temperature) of the nanocomposites increased as the PVB content increased. The change in the positive temperature coefficient was related to the morphological differences (i.e., the period of lamellar twisting) in the nanocomposites. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1022–1031, 2003     

Shear-induced crystallization of poly(phenylene sulfide)

The crystalline morphology of poly(phenylene sulfide) (PPS) isothermally crystallized from the melt under shear has been observed by polarized optical microscope (POM) equipped with a CSS450 hot-stage. The shish–kebab-like fibrillar crystal structure is formed at a higher shear rate or for a longer shear time, which is ascribed to the tight aggregation of numerous oriented nuclei in the direction of shear. The crystallization induction time of PPS decreases with the shear time, indicating that the shear accelerates the formation of stable crystal nuclei. Under shear, the increase of spherulite growth rate results from highly oriented chains. The melting behavior of shear-induced crystallized PPS performed by differential scanning calorimetry (DSC) shows multiple melting peaks. The lower melting peak corresponds to melting of imperfect crystal, and the degree of crystal perfection decreases as the shear rate increases. The higher melting peak is related to the orientation of molecular chains. These oriented molecular chains form the orientation nuclei which have higher thermal stability than the kebab-like lamellae that are developed later. A new model based on the above observation has been proposed to explain the mechanism of shish–kebab-like fibrillar crystal formation under shear flow.     

Effects of liquid–liquid phase separation on crystallization kinetics and morphology of isotactic polypropylene/poly (ethylene-co-octene) in-reactor alloy

In this work, we investigated the effects of liquid–liquid phase separation (LLPS) on the crystallization kinetics and morphology of isotactic polypropylene/poly (ethylene-co-octene) (iPP/PEOc) in-reactor alloy with polarized optical microscopy (POM), differential scanning calorimeter (DSC), scanning electron microscopy (SEM), wide angle X-ray scattering (WAXS) and small angle X-ray scattering (SAXS) methods. Based on crystallization kinetics analysis by Avrami equation, we found that the overall crystallization rate was almost independent on LLPS time, whereas was strongly dependent on crystallization temperature. However, by combination with POM, we found that the LLPS played two opposite roles on the overall crystallization rate, i.e. the nucleation rate decreased and the spherulite growth rate increased as increasing LLPS time. It is due to the nucleation rate was dominated by fluctuation-assisted nucleation mechanism and the growth rate was dominated by diffusion-controlled growth. Furthermore, the spherulite size and PEOc domain size of iPP/PEOc in-reactor alloy were significantly dependent on LLPS time; however, the crystallinity was almost not dependent on LLPS time.     

Effect of sepiolite on the crystallization behavior of biodegradable poly(lactic acid) as an efficient nucleating agent

To enhance the crystallization kinetics of poly(lactic acid) (PLA), fibrous sepiolite was explored for nucleating the crystallization of PLA. PLA/sepiolite nanocomposites were prepared via the melt‐extrusion method. The effect of sepiolite on the crystallization behavior, spherulite growth and crystal structure of PLA were investigated by means of differential scanning calorimetry (DSC), polarized optical microscope (POM), wide angle X‐ray diffraction (WAXD), Fourier transform infrared (FTIR), and scanning election microscope (SEM). On the basis of DSC and POM results, the overall crystallization kinetics of PLA/sepiolite nanocomposites were significantly enhanced leading to higher crystallinity and nucleation density, faster spherulite growth rate (G) and lower crystallization half‐time (t_1/2) compared with the neat PLA. Under non‐isothermal conditions, the PLA blend comprising 1.0 wt% of sepiolite still revealed two crystallization peaks upon cooling at a rate of 35°C/min. Above phenomena strongly suggested that sepiolite was an effective nucleating agent for PLA. FTIR and WAXD analyses confirmed that the crystal structure of PLA matrix was the most common α‐form. SEM micrographics illustrated the fine three‐dimensional spherulite structures with the lath‐shape lamellae regularly arranged in radial directions. POLYM. ENG. SCI., 55:1104–1112, 2015. © 2014 Society of Plastics Engineers     

Microscopy and microbeam X-ray analyses in poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with amorphous poly(vinyl acetate)

Double ring-banded spherulites of biodegradable poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV with 12 wt% 3HV) blending with 30 wt% amorphous poly(vinyl acetate) (PVAc) were examined using polarized light optical microscopy (POM), scanning electron microscopy (SEM), atomic-force microscopy (AFM) and micro-beam X-ray diffraction. A ring-banded spherulite of PHBV/PVAc 70/30 blend was linearly scanned across the bands in 5 μm steps by means of micro-beam X-ray diffraction. Solvent-etching and fracturing were utilized for probing the interior lamellar textures of the blend samples. Detail interior lamellar orientations in bulk film of PHBV three-dimensional ring-banded spherulites were revealed. SEM and micro-beam X-ray diffraction results suggest that the PHBV lamellar orientation gradually change along the radial growth direction with right-handed rotation sense. The blending effect in band pattern (width and regularity) of PHBV/PVAc blend was discussed.     

Improvement of microstructures and properties of poly(lactic acid)/poly(ε‐caprolactone) blends compatibilized with polyoxymethylene

Incompatibility of poly(lactic acid)/poly(?‐caprolactone) (PLA/PCL) (80:20) and (70:30) blends were modified by incorporation of a small amount of polyoxymethylene (POM) (≤3 phr). Impact of POM on microstructures and tensile property of the blends were investigated. It is found that the introduction of POM into the PLA/PCL blends significantly improves their tensile property. With increasing POM loading from zero to 3 phr, elongation at break increases from 93.2% for the PLA/PCL (70:30) sample to 334.8% for the PLA/PCL/POM (70:30:3) sample. A size reduction in PCL domains and reinforcement in interfacial adhesion with increasing POM loading are confirmed by SEM observations. The compatibilization effect of POM on PLA/PCL blends can be attributed to hydrogen bonding between methylene groups of POM and carbonyl groups of PLA and PCL. In addition, nonisothermal and isothermal crystallization behaviors of PLA/PCL/POM (70:30:x) samples were investigated by using differential scanning calorimetry and wide angle X‐ray diffraction measurements. The results indicate that the crystallization dynamic of PLA matrix increases with POM loadings. It can be attributed to the fact that POM crystals have a nucleating effect on PLA. While crystallization temperature is 100 °C, crystallization half‐time can reduce from 9.4 to 2.0 min with increasing POM loading from zero to 3 phr. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46536.     

Confined crystallization morphology of poly(ϵ‐caprolactone) block within poly(ϵ‐caprolactone)–poly(l‐lactide) copolymers

The confined crystallization of poly(?‐caprolactone) (PCL) block in poly(?‐caprolactone)–poly(l ‐lactide) (PCL‐PLLA) copolymers was investigated using differential scanning calorimetry, polarized optical microscopy, scanning electronic microscopy and atomic force microscopy. To study the effect of crystallization and molecular chain motion state of PLLA blocks in PCL‐PLLA copolymers on PCL crystallization morphology, high‐temperature annealing (180 °C) and low‐temperature annealing (80 °C) were applied to treat the samples. It was found that the crystallization morphology of PCL block in PCL‐PLLA copolymers is not only related to the ratio of block components, but also related to the thermal history. After annealing PCL‐PLLA copolymers at 180 °C, the molten PCL blocks are rejected from the front of PLLA crystal growth into the amorphous regions, which will lead to PCL and PLLA blocks exhibiting obvious fractionated crystallization and forming various morphologies depending on the length of PLLA segment. On the contrary, PCL blocks more easily form banded spherulites after PCL‐PLLA copolymers are annealed at 80 °C because the preexisting PLLA crystal template and the dangling amorphous PLLA chains on PCL segments more easily cause unequal stresses at opposite fold surfaces of PCL lamellae during the growth process. Also, it was found that the growth rate of banded spherulites is less than that of classical spherulites and the growth rate of banded spherulites decreases with decreasing band spacing. © 2019 Society of Chemical Industry     

Banded spherulites of electrospun poly(trimethylene terephthalate)/carbon nanotube composite mats

The crystallization of poly(trimethylene terephthalate) (PTT) composites containing carbon nanotubes (CNTs) were studied in this work. The electrospinning technology was employed successfully to fabricate thin film samples with well‐embedded CNTs for spherulite observations using atom force microscopy. The results show that the composites present a higher overall crystallization rate than that of the neat PTT due to the nucleation effect of the CNTs. Banded spherulites can be observed on both the neat PTT and the composites. The presence of CNTs does not change the twisting mode of PTT crystal, but reduces band spacing and twist period. This is attributed to the enhanced fold staggering level of lamellae caused by the narrowed lamellae size and accelerated spherulite growth, which is further confirmed by analysis through secondary nucleation theory. Copyright © 2011 Society of Chemical Industry     

Structure of blown films of polyethylene/polybutene‐1 blends

The structure of blown films of blends of low‐density polyethylene (PE‐LD) and isotactic polybutene‐1 (iPB‐1) with different content of iPB‐1 was investigated using wide‐ and small‐angle X‐ray scattering (WAXS and SAXS), transmission electron microscopy (TEM), and polarizing optical microscopy (POM). TEM proves formation of a matrix–particle phase structure due to immiscibility of the blend components. Within the iPB‐1 particles, needle‐like crystals with c‐axis orientation were observed. The PE‐LD matrix showed two populations of crystals. WAXS data indicate that the majority of crystals were oriented with the c‐axis perpendicular to machine direction (MD), while SAXS data prove additional presence of stacks of lamellae, oriented parallel to MD. Quantitative birefringence measurements showed that the majority of molecule segments were oriented in the direction of the circumference of the film, confirming the WAXS data. The crystal orientation has direct impact on mechanical properties, which was demonstrated by measurement of the anisotropy of the modulus of elasticity. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Effects of crystallization behavior on morphological change in poly(trimethylene terephthalate) spherulites

In poly(trimethylene terephthalate) (PTT) spherulites during isothermal crystallization, the morphological changed from an axialite/or elliptical banded spherulite to banded spherulite and then non-banded spherulite with temperature decreasing were studied by following the lamellar growth behaviors. We report lamellar growth mechanism on varied crystallization temperature, which explicitly probes the link between microscopic structure and macroscopic morphology in the development of patterns. Fibrillation of the edge-on lamellae was observed on the surfaces of axialite and the convex bands of banded spherulite. Terrace-like lamellae were observed on the surface of the non-banded spherulite and the concave bands of banded-spherulite. In thin film crystallization, PTT banded spherulite exhibits a texture of alternate edge-on and flat-on lamellae, wavy-like surface and rhythmic growth. The deceleration of growth rate takes place in convex bands with a growth habit of fibrillation of the edge-on lamellae for emerging ridge surface. On the other hand, the acceleration of growth rate appears in concave bands with a growth habit of terrace-like lamellae for emerging valley surface. The alternating growth mechanism of the lamellae was considered to be related with the formation of spatiotemporal self-organization patterns far from equilibrium. In order to explain the rhythmic growth and periodic growth of the lamellae, we may conjecture that the emergence of PTT banded spherulite in thin film crystallization is associated with an oscillatory dynamics of the spherulite growth front driven by latent heat diffusion. We present some tentative ideas on the possibility of band-to-nonband (BNB) morphological transition, which might be analogous with the second order transition in non-equilibrium phase transition.     

Nanostructure of Potato Starch,Part I: Early Stages of Retrogradation of Amorphous Starch in Humid Atmosphere as Revealed by Simultaneous SAXS and WAXS

Crystallization experiments on amorphous, injection-molded starch in a humid atmosphere are reported. The crystallization mechanisms have been studied using simultaneous SAXS and WAXS during a temperature stepwise increase. In contrast to the crystallization of linear synthetic polymers, in starch the WAXS peaks are observed at low temperature before the appearance of the SAXS maximum. The initial state of crystallization is dominated by the amylose (AM) component of the potato starch alone. After the initial formation of large (16 nm) uncoordinated individual crystallites, stacks of lamellae and finally, an insertion of thinner lamellae within the stacks are observed. Results indicate that only if all AM is converted into a semicrystalline structure and if the secondary starch network of double helices of AM and amylopectin (AP) is molten by a temperature increase above 70°C, crystallization of AP also occurs. Because the AM crystals act as nuclei for the AP component, a common superstructure is developed. Within a spherulite, alternating AM and AP lamellae develop radially from the center of the AP molecule. Results suggest that the AM is distributed inhomogeneously with respect to the AP molecules, leaving approximately one half of the AP fraction free, which means not crystallized to a spherulitic structure together with AM.     

Poly(lactide)-based supramolecular polymers driven by self-complementary quadruple hydrogen bonds: construction,crystallization and mechanical properties

A series of poly(lactide) (PLA)-based supramolecular polymers based on linear PLLA-b-PCL-b-PLLA triblock copolymers (PLLA, poly(l -lactide); PCL, poly(ε-caprolactone)) or/and three-arm star (PCL-b-PDLA)₃ block copolymers (PDLA, poly(d -lactide)) were synthesized. The effects of the structure and composition on crystal structure, crystallization behavior, spherulite morphology and mechanical properties of the synthesized supramolecular polymers were investigated. The results of DSC and polarized optical microscopy indicated that the supramolecular polymer exhibited poor crystallization ability with respect to PCL/PLA block copolymer, and the crystallinity of the supramolecular polymer with alternating PCL/PLA multiblock structure was stronger than that with similar crosslinked network structure. The presence of molten PCL blocks disturbed the orientation of lamellae, forming spherulites with feather-like dendrites, and ring-banded spherulites were observed as the molecular weight of the PLA blocks increased. The results of tensile tests demonstrated that supramolecular polymers with larger molecular weight of PLA blocks showed the pronounced ductile fracture. On this basis, stereocomplexed supramolecular polymers were also synthesized, and it was found that the stereocomplex crystals had a significant impact on the crystallization and mechanical properties of the supramolecular polymers. Therefore, in this work a novel technique for manufacturing toughened PLA-based material and tuning its performances is proposed, which may promote the application of PLA-based materials in more fields. © 2022 Society of Industrial Chemistry.