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Biomedical applications of polymers require precise control of the solid-state structure, which is of particular interest for biodegradable copolymers. In this work, we evaluated the influence of crystallization conditions on the comonomer exclusion/inclusion balance of biodegradable poly(butylene succinate- ran -butylene adipate) (PBSA) isodimorphic random copolymers. Regardless of the crystallization conditions, the copolymers retain their isodimorphic character, displaying a pseudo-eutectic behavior with crystallization in the entire composition range. This illustrates the thermodynamic nature of the isodimorphic behavior for PBSA random copolymers. However, depending on the composition, the crystallization conditions affect the exclusion/inclusion balance of the comonomers. Fast cooling favors butylene adipate (BA) inclusion inside the poly(butylene succinate) (PBS) crystals, whereas isothermal crystallization strongly limits it. PBA-rich compositions behave differently. Both fast and slow crystallization formed the β-phase, whereas BS unit inclusion is favored independently of the cooling conditions. During successive self-nucleation and annealing, the BA inclusion is intermediate between non-isothermal and isothermal conditions, while the crystalline structure of the PBA phase changes from the β-phase to the more stable α-phase. We propose a simple crystallographic model to explain the changes in the unit cell dimension of the copolymers.

Poly(lactic acid) (PLA) is one of the most promising alternatives for petrochemical-based plastics. Crystallization mediation provides the simplest and most practical approach for enhancing the properties of PLA. Here, recent advances in understanding the relationship between crystalline structure and properties of PLA are summarized. Methods for manipulating crystallization towards high-performance PLA materials are introduced., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Self‐healing polyamide multiblock copolymer with robust mechanical properties is highly desired. Here, an alicyclic diamine monomer, isophoronediamine (IPDA), with asymmetric structure and substantial steric hindrance was incorporated into the backbone of poly(ether‐b‐amide) multiblock copolymer. Based on the phase‐lock effect, the mechanical properties and segmental mobility of copolymers can be modulated on a large scale via adjusting the molecular weight of hard segments. An extraordinary tensile strength of 32.0 MPa and an excellent elongation at break of 1881 % were simultaneously achieved, which leaded to a record‐high toughness of 328.9 MJ m−3 for self‐healable polyamide elastomers. The synergism between the dynamic H‐bonding networks and the diffusion of polymer chains contributed to a balance between the mechanical performance and self‐healing efficiency of copolymers. Due to the adjustable mechanical performance, rapid scratch self‐healing ability and superior impact resistance, the resultant copolymers showed great potential in the fields of protective coatings and soft electronics. [ABSTRACT FROM AUTHOR]

We studied the crystallization of nearly "homogeneous" polyethylene glycol (PEG) networks prepared by end-crosslinking of tetra-armed PEG. The influence of stretching ratio and strand length on the melting and crystallization temperature was investigated. The relation of melting temperature and elongation ratio verifies the thermodynamic theories of strain-induced polymer crystallization. [ABSTRACT FROM AUTHOR]

This study examines the miscibility and mechanical properties of isotactic polypropylene (iPP) and olefin block copolymer (OBC) blends (70/30 wt %). The blends exhibit phase-separated morphology. The OBC domain size decreases with increasing the 1-octene content in the soft segment. The crystallization, melting behavior, and the long spacing of the iPP component in the blends are nearly the same as those of neat iPP, while the T g of the iPP component shifts slightly to lower temperature. 'Blocky' OBC is immiscible with iPP, while the soft segment rich polymers in OBC could be partially miscible with iPP. The impact strength of the blends is greatly increased with increasing the 1-octene content in the OBC soft segment. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012 [ABSTRACT FROM AUTHOR]

The morphology evolution and rheological response of a near-critical composition polybutadiene/polyisoprene blend after the cessation of steady shear was studied with an ARES rheometer and a shear light scattering photometer equipped with an optical microscope in this work. The relationship between the morphology of the blend during the relaxation after the cessation of steady shear with different shear rates and their corresponding rheological properties was successfully established. It was found that the different shear-induced morphologies under steady shear would relax to the equilibrium states via varied mechanisms after the shear cessation. The average size of the dispersed domains in the coarsening process was influenced by the pre-shear history. The results indicated that the pre-shear history could slow down the growth rate of phase domains during the coarsening process. It had effect on the coarsening mechanism on the early stage of relaxation after the cessation of very strong shear when the homogenization effects were strong, but no effect on the late stage. The storage modulus G′ increased significantly in the breakup process of the string-like phase. After all the string-like structures were broken up into small ellipsoids, then G′ gradually decreased and finally approached to an invariant value. The characteristic rheological behavior can be attributed to the different structure on the relaxation process. [ABSTRACT FROM AUTHOR]

Abstract: In this paper, the chain packing and phase transition of comb-like polymer has been deeply analyzed with N-hexacosylated polyethyleneimine (PEI26C) as a template, fabricated through the reaction between n-hexacosyl bromide and PEI in a homogenous solution. The effect of long alkyl groups on the chain packing and phase transition of PEI26C was systematically investigated by synchrotron X-ray scattering and variable-temperature FTIR spectroscopy. PEI26C comb-like polymer exhibited an interesting structure-evolution process, and phase transformation from orthorhombic (β O ), monoclinic (β M ), to hexagonal (α H ) phase, and finally to amorphous state was demonstrated, indicating that large alkyl domains induced the complicated structures. Size-depended phase transition behavior provides an insight into the formation of metastable structure during the early stage of polymer crystallization. [Copyright &y& Elsevier]

Abstract: Stimuli-responsive polymeric materials can adapt to various surrounding environments, converting chemical and biochemical changes into optical, electrical and thermal signals, or changing wettability and adhesion properties upon external stimuli. Herein we report a cotton fabric modified with a thermo-responsive polymer, Poly(N-isopropylacrylamide) (PNIPAAm). 1H solid-state NMR techniques were used to characterize the molecular structure and dynamics of the PNIPAAm brushes, while still grafted on the cotton fabric surfaces, avoiding un-grafting destructive procedures. The results demonstrate that the motion of the grafted PNIPAAm brushes is restricted as the temperature rises above the low critical solution temperature (LCST), which was estimated to be ∼34 °C. Variable temperature (VT) experiments were used to investigate the nature of the hydrophilic-hydrophobic transitions of the grafted polymer. The 1H solid-state NMR techniques used proved to be an extremely sensitive and precise way to probe in-situ the LCST transition of the PNIPAAm brushes, while still grafted on cotton fibres. This work presents a high potential synthesis and analysis route towards stimuli-responsive cotton fibres which can find exceptional applications as novel intelligent fabrics for the textile related industries. [Copyright &y& Elsevier]

Abstract: In order to study the relationship between structure and properties, multiblock copolymers composed of poly(butylene succinate) (PBS) and poly (1,2-propylene succinate) (PPSu) have been synthesized by chain-extension at various molar ratios of hexamethylene diisocyanate (HDI) to polyester-diols, which have been abbreviated as R-values in this paper. Molecular weights of soluble fractions, gel fractions and crosslink densities have been determined. Thermal properties, mechanical properties and biodegradability have been studied and correlated with R-values. Crystallization of copolymers becomes difficult with increasing R-value. Tensile strength, flexural strength and flexural modulus tend to increase with increasing R-value up to 1.2, and vary little when R-value increases from 1.2 to 1.3, then decrease with further increase in R-value. Impact strength achieves a maximum value at R-value of 1.3. Biodegradation rate reaches a minimum value when R-value is 1.1. Biodegradation has been studied systematically by attenuated total reflectance Fourier transform infrared (ATR-FTIR), 1H NMR and SEM. [ABSTRACT FROM AUTHOR]

Abstract: Isothermal crystallization of isotactic polypropylene (iPP)/organic montmorillonite (OMMT) binary composite under shear field was investigated by in situ polarized optical microscopy, rheometry and transmission electron microscopy. When shear strain was small, shear flow could enhance the crystallization of iPP, and the crystallizing entity was spherulitic in iPP/OMMT composite in which the OMMT content was below the percolation threshold. With shear strain increasing, the orientation extent became stronger and cylindrites and strings of spherulites appeared in these samples. However, for iPP/OMMT composite with OMMT content higher than the percolation threshold, when the shear strain was not big enough to destroy the fillers network in the matrix, the crystallization of iPP was similar with that of the un-sheared sample. When shear strain was large enough, the fillers network was destroyed and clay layers were aligned along the flow direction. There formed oriented crystals including cylindrites and strings of spherulites, which were much smaller in size than those formed in the previous case, because the aligned clay layers acted as heterogeneous nucleation agents to promote crystallization of iPP. [Copyright &y& Elsevier]

Abstract: Syndiotactic polypropylene (sPP) fiber was prepared by melt spinning with the taken-up velocity of 200–700m/min, the conformation and crystallization of which were systematically investigated by a combination of Fourier transform infrared (FTIR) spectroscopy, wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). The results indicated that sPP fibers consist of form I crystal with helical conformation at the spinning velocity of 200–300m/min, and the crystallinity and orientation are improved with the increase of spinning velocity in this range. As the spinning velocity exceeds 300m/min, sPP fibers contain mainly mesophase with trans-planar conformation and the content of form I decreases correspondingly. The crystallization behavior of sPP fiber with spinning velocity is different from that of most other crystalline polymers, i.e., the theory of orientation-induced crystallization is not well conformed to. For sPP, form I comprising of helical conformation is thermodynamically stable, though extensional stress can lead to transition from helical to trans-planar conformation, which is not favorable for the crystallization of form I. [Copyright &y& Elsevier]

Abstract: Order–disorder transition (ODT) behavior in eicosylated polyethyleneimine (PEI20C) comblike polymer obtained by grafting n-eicosyl group on polyethyleneimine backbone was systematically investigated by the combination of differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), Fourier transform infrared (FTIR) spectroscopy as well as solid-state high resolution nuclear magnetic resonance (NMR) spectroscopy. DSC investigations showed two obvious transitions, assigned to the transitions (1) from orthorhombic to hexagonal and (2) from hexagonal to amorphous phase, respectively. These transitions are induced by the variations of alkyl side chain conformation and packing structure with temperature changing, which consequently lead to the destruction of original phase equilibrium. The ODT behavior can also be confirmed by spectroscopic methods like WAXD, FTIR and NMR. The ordered structure and the transition behavior of the alkyl side chains confined by the PEI backbone are obviously different from those of pristine normal alkanes. The transition mechanism of ODT and the origin of the phase transition behavior in PEI20C comblike polymer were discussed in detail in this paper. [Copyright &y& Elsevier]

Abstract: The changes of conformation and crystalline structure of long chain branched isotactic polypropylene (LCB-iPP) under different crystallization temperatures and the effects of their special molecular architecture on the crystallization behavior were investigated by a combination of Fourier transform infrared spectroscopy (FT-IR), wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). In these polymers, long chain branching was introduced via in situ polymerization of polypropylene and an asymmetric diene monomer using the metallocene catalyst technology. Through the characterization of the specific IR band variation, it was proved that the conformational orders of helical sequences of LCB-iPP show great changes in different crystallization temperature ranges. In lower crystallization temperature range (100–130°C), the intensities of all regular helical conformation bands of LCB-iPP increase with the increasing crystallization temperature and the regular helical conformation bands with more monomer units increase faster than that with less monomer units. In higher crystallization temperature range (130–150°C), the intensities of all regular helical conformation bands of LCB-iPP decrease with the increasing crystallization temperature and the regular helical conformation bands with more monomer units decrease faster than that with less monomer units. The results of WAXD and DSC showed that LCB-iPP crystallizes from the melt as a mixture of α and γ forms. The content of the γ form increases with the increasing crystallization temperature, reaches a maximum value at 130°C, and then decreases with a further increase of the temperature. At the same time, the crystallization of γ form is favored by the presence of the LCB structure of iPP. Moreover, the transitional temperatures of different helical conformations and crystallization structures of LCB-iPP show obvious correlations. [Copyright &y& Elsevier]

Abstract: Regular structures in polymer melt play important roles during crystallization and subsequently influence performances of polymer materials. In the present work, differential scanning calorimetry (DSC) and variable temperature Fourier transform infrared spectroscopy (VT-FTIR) were used to characterize the variations of regular structures in melt of syndiotactic polypropylene (sPP) during heating. It was found that during heating, the structural transition in sPP melt undergoes four stages: (1) destruction of long regular structures; (2) formation of short regular structures; (3) transition from short regular structures to isotropic state; and (4) isotropic state. These regular structures in sPP melt have distinct memory effects on the crystallization behaviors. By using Flory''s RIS model, it was found that in final isotropic state, the most common conformers are ttgg and tttt, corresponding to helical and planar–zigzag conformations, respectively. These findings are helpful to deeply understand the essence of structures in sPP melt and microstructure variations during melting. [Copyright &y& Elsevier]

Abstract: It is well known that a so-called “three-dimensional filler network structure” will be constructed in the polymer/layered silicate nanocomposites when the content of layered clay reaches a threshold value, at which the silicate sheets are incapable of freely rotating, due to physical jamming and connecting of the nanodispersed layered silicate. In this article, the effect of such clay network on the mobility and relaxation of macromolecular chains in isotactic polypropylene(iPP)/organoclay nanocomposites was investigated in detail with a combination of DMTA, DSC, TGA, TEM, rheometry and melt flow index measurements. The main aim is to establish a relationship between the mesoscopic filler network structure and the macroscopic properties of the polymer nanocomposites, particularly to explore the role of the clay network on the mobility and relaxation of macromolecular chains. It was found that the nanodispersed clay tactoids and layers play less important or dominant roles on the mobility of iPP chains depending on the formation of percolating filler network. The turning point of macroscopic properties appeared at 1wt% organoclay content. Before this point, the effect of organoclay can be negligible, and the increase of chain mobility was ascribed to the decrease of molecular weight of polymer chains, as commonly occurs during dynamic melt processing; after this point, however, a reduced mobility of chains and a retarded chain relaxation were observed and attributed to the formation of a mesoscopic filler network. The essential features of such a mesoscopic organoclay network were estimated and discussed on the basis of stress relaxation and structural reversion measurements. A schematic model was proposed to describe the different relaxation and motion behaviors of macromolecular chains in the unfilled polymer and the filled hybrids with partial and percolated organoclay networks, respectively. [Copyright &y& Elsevier]

The supermolecular structures of iPP fiber/matrix composites as a function of crystallization temperature were studied by means of optical microscopy. The results show that, even though partial melting of the iPP fibers is in favor of initiating the β-iPP crystal growth, the interfacial morphology of iPP single-polymer composites induced by its own fiber depends strongly on the crystallization temperature. It was found that transcrystalline structures of negative radial βIII-iPP or banded βIV-iPP can be produced within the crystallization temperature range 105–137°C, while transcrystallization zone of pure negative radial αII-iPP crystals is observed at higher crystallization temperature, e.g. 141°C. On the other hand, the surrounding iPP spherulites grown from the bulk are composed of α-iPP in the whole crystallization temperature range. However, the optical character of the spherulites is controlled by the thermal condition. [Copyright &y& Elsevier]

Abstract: A series of rigid-rod poly(p-benzamide) polymers (PBA) with different length of flexible alkyl side chains, denoted as PBA(n)Cs, have been prepared by N-alkylation method. The alkyl side chain lengths varied from decyl (n=10) to octadecyl (n=18), with an interval of two carbon atoms. The packing mode and conformational transition of the alkyl side chains of the prepared PBA derivatives were characterized by wide-angle X-ray diffraction (WAXD), differential scanning calorimertry (DSC), and Fourier transform infrared spectroscopy (FTIR). WAXD results revealed that the derivatives form layered structure in which the distance between the backbones depends on the length of alkyl side chains. DSC studies indicated that melting transition temperature of PBA(n)Cs increases accordingly with increasing the alkyl chain length of the substituents. Meanwhile, DSC results proved that as the carbon atom number of the side group exceeds 14, alkyl side chains in PBA(n)Cs tend to crystallize FTIR spectroscopic investigation showed that the all-trans zigzag conformation is the most stable state for the alkyl side chain in PBA18C comb-like polymer. Temperature variation caused the reversible transition between trans and gauche conformational states of the side octadecyl group, and in turn made the molecular chain packing mode of PBA18C comb-like polymer undergo an reversible transformation from ordered packing to disordered packing. [Copyright &y& Elsevier]

Homogeneity fiber/matrix composites of isotactic polypropylene (iPP) were prepared with both partially carbon-coated and non-carbon-coated iPP fibers. Their morphologies produced by melt recrystallization were studied by means of polarized optical microscopy. The results show that through vacuum evaporating a thin carbon film partially on the surface of iPP fiber, the nucleation ability of the molten iPP matrix during the course of recooling has been enhanced tremendously. The early formation and high density of the iPP row nuclei formed along the partially carbon-coated iPP fibers lead to the formation of an apparent iPP transcrystalline zone in the vicinity of its precoated fiber. The high nucleation ability of the carbon-coated iPP fiber towards its homogeneity matrix may originate from the surface fixing effect of the vacuum evaporated carbon layer on the polymer samples. [Copyright &y& Elsevier]

• FC occurs when a polymer is divided in a large number of microdomains (MDs). • When the number of heterogeneities in bulk equals the number of MDs, FC occurs. • The injection of nucleating agents or self-nuclei in every MD eliminates FC • Nucleation goes from heterogeneous to homogeneous by increasing confinement. • Crystallization kinetics can change from sigmoidal to first order by confinement. The crystallization of heterogeneously nucleated bulk polymers typically occurs in a single exothermic process, within a narrow temperature range, i.e., a single exothermic peak is detected by differential scanning calorimetry when the material is cooled from the melt. However, when a bulk semicrystalline polymer is subdivided or dispersed into a multitude of totally (or partially) isolated microdomains (e.g., droplets or cylinders), in number comparable to that of commonly available nucleating heterogeneities, several separated crystallization events are typically observed, i.e., fractionated crystallization. This situation is often found for the minor crystallizable component in immiscible blends. When the bulk polymer is dispersed into a number of microdomains that is several orders of magnitude higher than the available number of heterogeneities within it, most microdomains will be heterogeneity-free. In these clean microdomains the nucleation can occur by contact with the interfaces (i.e., surface nucleation) or by homogeneous nucleation inside the microdomain volume. These cases can be easily encountered in cylinders or spheres within strongly segregated block copolymers, or in infiltrated polymers within nanopores of alumina templates. In this work, a comprehensive review of the known cases of fractionated crystallization is provided. The changes upon decreasing microdomain sizes from a dominant single heterogeneous nucleation, through fractionated crystallization, to surface or homogeneous nucleation are critically reviewed. Emphasis is placed on the common features of the phenomenon across the different systems, and thus on the general conclusions that can be drawn from the analysis of representative semicrystalline polymers. The origin of the fractionated crystallization effects and their dramatic consequences on the nucleation and crystallization kinetics of semicrystalline polymers are also discussed. [Display omitted] [ABSTRACT FROM AUTHOR]

Review: 231 refs. [ABSTRACT FROM AUTHOR]