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Regulation of phase structure has been recognized as one of the most effective ways to fabricate self-healing polymers with high mechanical strength. The mechanical properties of the resultant polymers are certainly affected by the size of separated phase domain. However, the study on this aspect is absence, because it can hardly exclude the influence of variation in monomer proportion required for tuning the separated phase size. Here, we report the first study on tuning the phase size through reversible addition-fragmentation chain transfer (RAFT) polymerization without changing the proportion of monomers. As expected, the size of separated phase has been successfully mediated from 15 nm to 9 nm by tuning the molecular weight of the chain transfer agent. It is found that the mechanical strength and the self-healing efficiency of the resultant polymers increase simultaneously with the decrease of phase size. The study on the formation kinetics of hydrogen bonds reveals that the decrease of phase size can facilitate the re-bonding rate of hydrogen bonds, even if the migration of polymer chains is restricted. [ABSTRACT FROM AUTHOR]

Poly(lactic acid) (PLA) as a bio-based polymer with biodegradability and biocompatibility has attracted much attention. To manipulate its properties for different applications, regulation of crystal structure and crystalline morphology becomes an attractive research topic. In this work, the structure evolution of layered samples containing an amorphous poly(D-lactide) (PDLA) layer and a crystalline poly(L-lactide) (PLLA) layer with highly oriented edge-on α lamellar crystals after annealing at 150 °C or/and after melt-recrystallization has been studied by AFM, FTIR, and TEM combined with electron diffraction. The results demonstrate that melt recrystallization of the as-prepared sample leads to the formation of abundant randomly oriented PLA stereo-complex (PLA SC) crystals. Annealing at 150 °C results in the formation of a small amount of oriented PLA SC crystals at the interface. These PLA SC crystals show great impact on the recrystallization behavior of sample after melting at 190 °C and then crystallizing at 90 °C. First, they impede the mutual diffusion of the overlying PDLA and underlying PLLA, and thus reduce their stereocomplexation ability as manifested by the decreased amount of PLA SC crystals. Second, they act as substrate to initiate the epitaxial crystallization of the overlying PDLA and underlying PLLA, which ensures the production of a highly oriented structure of PDLA and PLLA after melt recrystallization again. [ABSTRACT FROM AUTHOR]

The effect of freezing layer on the crystallization kinetics of poly(ε-caprolactone) (PCL) thin and ultrathin films was investigated by monitor the growth process of it on oriented polyethylene (PE) and CaF2 with and without freezing layer, respectively. It was found that the PCL films with similar thicknesses crystallize much faster on oriented PE than on CaF2 substrate. For example, the crystallization rate constant of a 102 nm thick PCL film decreases tremendously by 3 orders of magnitude from 1.1×10−1 on PE substrate at 50 °C to 7×10−4 on CaF2 surface at 40 °C. Moreover, the crystallization of PCL accelerates on CaF2 surface while slows down at PE surface with increasing film thickness. The ultrathin films of PCL with thickness less than 14 nm exhibits the fastest crystallization rate on oriented PE with a rate constant of about 3.5×10−1, which is 3 times higher than that of a ca. 50 nm thick film. This illustrates the great influence of freezing layer on the crystallization process of PCL. The freezing layer thickness of PCL on PE is estimated to be in the range of 14–17 nm. Taking the radius of gyration (Rg ∼ 15.6 nm) of the used PCL material into account, the obtained results may imply the existence of a correlation between the Rg of PCL and its freezing layer thickness at PE substrate. [ABSTRACT FROM AUTHOR]

Despite growing interest in nano-sized fillers, micro-sized fillers with desired compatibility are still used for reinforcing rubbers, owing to their lower production cost and easier processing relative to nano-sized fillers. Especially, the abundant and eco-friendly clay minerals are recognized as the materials of the twenty-first century. Herein, illite, a naturally occurring clay having dimension in micrometric scale, has been selected as filler to reinforce the SBR. To improve the compatibility of illite with SBR, the illite was modified by either bis[3-(triethoxysilyl)propyl] tetrasulfide (Si69-illite) or 3-mercaptopropyltriethoxysilane (KH580-illite). The interfacial interactions of SBR composites filled with pristine illite (illite/SBR) and Si69-illite (Si69-illite/SBR), or KH580-illite (KH580-illite/SBR) were characterized by bound rubber content and Payne effect measurements, while dynamic hysteresis losses of these uncured and cured composites were also analyzed under various strain amplitudes. It was found that the filler-rubber interactions were greatly improved for Si69-illite/SBR and KH580-illite/SBR systems compared to the illite/SBR composite. This leads to an increment of modulus at 300% strain of the composites from 3.46 MPa for illite/SBR to 7.70 MPa for Si69-illite/SBR and 12.96 MPa for KH580-illite/SBR. Moreover, lower rolling resistance and better wear resistance without compromising wet traction of Si69-illite/SBR and KH580-illite/SBR have been achieved. This demonstrates the high possibility of Si69 and KH580 modified illites as promising alternative fillers for reinforcing rubbers. [ABSTRACT FROM AUTHOR]

Ferroelectric poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE))/semiconducting poly(3-hexyl thiophene) (P3HT) blend systems have drawn great attention with their potential use for electronic applications, particularly non-volatile memory devices. It is essential to grasp a full understanding of the crystallization habits of the two polymers on different substrates for purposeful control of the structures of the blend and therefore the properties of the devices. Here, the effects of structure and morphology of the blend films generated at different substrate surfaces on the ferroelectric and switching properties of related devices are reported. It is identified that P(VDF-TrFE)/P3HT blend films prepared on graphene substrate show not only an obvious optimization in the ferroelectric behavior of P(VDF-TrFE), but also an enhancement of the charge transport within P3HT domains. By employing sandwich structure constructed by silver electrode and P3HT/P(VDF-TrFE) blend film on graphene substrate, high-performance ferroelectric memory devices have been obtained, which exhibit a great electrical switching behavior with high ON/OFF ratio of about 1000 and low coercive voltage of approximately 5 V. These findings provide useful guidance for fabricating high-performance ferroelectric memory devices. [ABSTRACT FROM AUTHOR]

Matrix/fiber composites of β-form isotactic polypropylene ( iPP) matrix and α- iPP or PA6 fibers were prepared by laminating technique under different preparation temperatures. The mechanical properties and interfacial morphologies of these composites were studied by tensile test, optical microscopy and scanning electron microscopy, respectively. The experimental results show that the tensile yield load and tensile modulus of β- iPP/PA6 matrix/fiber systems increased significantly at the expense of elongation at break. These mechanical properties show essentially no dependence on the sample preparation temperature. On the other hand, the mechanical properties of iPP matrix/fiber single polymer composites depend strongly on the sample preparation temperature. At low sample preparation temperature, e.g., 172 °C, the solid α- iPP fiber induces α- iPP crystallization, leading to the formation of α- iPP transcrystalline layer around the fiber. This results in a remarkable increment of the tensile yield load and tensile modulus. The elongation at break is also much better than that of the iPP/PA6 matrix/fiber system. It reflects a better interfacial adhesion of the single polymer composite compared with the iPP/PA6 composite. At higher sample preparation temperature, e.g., 174 °C or 176 °C, the partial surface melting of the oriented fiber allows interdiffusion of iPP molecular chains in the molten fiber and matrix melt. The penetration of matrix chains into the molten iPP fiber results in some iPP molecular chains being included partially in the recrystallized fiber and the induced β-transcrystalline layers. This kind of configuration leads to an improvement of interfacial adhesion between the fiber and matrix, which causes a simultaneous increase of the tensile yield load, tensile modulus and elongation at break of β- iPP. [ABSTRACT FROM AUTHOR]

The effect of PBS on the morphological features of PVDF has been investigated by optical and atomic force microscopies under various conditions. It was found that neat PVDF forms large γ form spherulites with extraordinarily weak birefringence at 170°C. Adding 30% PBS makes PVDF exhibit intrigued flower-like spherulitic morphology. The growth mechanism was explained by the decrease of the supercooling and the materials dissipation. Increasing the PBS content to 70% favors the formation of ring banded spherulites. Temperature dependent experiments verify the γ→ γ phase transition occurs from the junction sites of the α and γ crystals, while starts from the centers of α spherulites in the blends. Ring banded structures could be observed in neat PVDF, 70/30 blend and 30/70 blend when crystallized at 155°C, without γ crystals. The band period of PVDF α spherulites increases with crystallization temperature as well as the amount of PBS content. At 140°C, spherulites in neat PVDF lose their ring banded feature, while coarse spherulites consisting of evident lamellar bundles could be found in 30/70 blend. [ABSTRACT FROM AUTHOR]

Abstract: The growth behaviors of cross-hatched and lath-like lamellae of α-form spherulites and flat-on lamellae of β-form pherulites of isotactic polypropylene were studied with a high-temperature atomic force microscopy in situ and in real time. The growth rates of crystal lamellae in types I, II and mixed α-form spherulites and in β-form spherulites, as well as the spatial frequency of tangential branching, were measured. The frequency of tangential branching increases with decreasing crystallization temperature, while the growth rates of leading radial and tangential lamellae are approximately the same at a given temperature. Observations of as-crystallized materials demonstrated that the spacing and length of transverse lamellae is sufficient to differentiate among spherulite types. Height measurements in the melt near the growth surface indicate roles of molecular transport in the crystallization process. [Copyright &y& Elsevier]

A sample containing different regions with poly(ε-caprolactone) (PCL), oriented polyethylene (PE), and oriented isotactic polypropylene (iPP) films in contact with glass slide has been prepared to be observed in the same view field in an optical microscope and the crystallization of PCL in different regions during cooling from 80 °C down to room temperature at a rate of 1 °C·min−1 was studied. The results showed that the crystallization of PCL started first at the PE surface and then at the iPP surface, while its bulk crystallization occured much later. This indicates that though both PE and iPP are active in nucleating PCL, the nucleation ability of PE is stronger than that of iPP. This was due to a better lattice matching between PCL and PE than that between PCL and iPP. Moreover, since lattice matching existed between every (hk0) lattice planes of both PCL and PE but only between the (100)PCL and (010)iPP lattice planes, the uniaxial orientation feature of the used PE and iPP films resulted in the existence of much more active nucleation sites of PCL on PE than on iPP. This led to the fact that the nucleation density of PCL at PE surface was so high that the crystallization of PCL at PE surface took place in a way like the film developing process with PCL microcrystallites happened everywhere with crystallization proceeding simultaneously. On the other hand, even though iPP also enhanced the nucleation density of PCL evidently, the crystallization of PCL at iPP surface included still a nucleation and crystal growth processes similar to that of its bulk crystallization. [ABSTRACT FROM AUTHOR]

Poly(vinylidene fluoride) (PVDF) exhibits pronounced polymorphs. Its γ phase is attractive due to the electroactive properties. The γ-PVDF is however difficult to obtain under normal crystallization condition. In a previous work, we reported a simple melt-recrystallization approach for producing γ-phase rich PVDF thin films through selective melting and subsequent recrystallization. We reported here another approach for promoting the αγ′ phase transition to prepare γ-phase rich PVDF thin films. To this end, a stepwise crystallization and subsequent annealing process was used. The idea is based on a quick generation of a large amount of α-PVDF crystals with some of their γ-PVDF counterparts at suitable crystallization temperature and then annealing at a temperature above the crystallization temperature for enhancing the molecular chain mobility to overcome the energy barrier of phase transition. It was found that crystallizing the PVDF melt first at 152 °C for 4 h, then quenching to room temperature and finally annealing the sample at 160 °C for 100 h was the most efficient to produce γ-PVDF rich films. This is related to the melting and recrystallization of the α-PVDF crystals produced during quenching in the annealing process at 160 °C, which favors the formation of γ-PVDF crystals for triggering the αγ′ phase transition. [ABSTRACT FROM AUTHOR]

In this study, we demonstrate a novel method for fabricating polythiophene patterns, i.e., cylindrical holes and cylinders, through blending of a thermally curable polythiophene carrying with tertiary ester groups (PT- tert-ESTER) and poly(methyl methacrylate) (PMMA), followed by thermal conversion of the PT- tert-ESTER to an insoluble polythiophene via low-temperature cleavage of the tertiary ester groups and removal of the PMMA component via ultraviolet degradation. We show that the surface polarity of substrates, the mass ratio of PT- tert-ESTER to PMMA in the blend solutions as well as the concentration of the blend solutions strongly influence the formation of the polythiophene patterns. Cylindrical holes are more readily formed on less polar substrates when a PT- tert-ESTER dominated blend solution is used, while cylinders are more readily formed on more polar substrates when a PMMA dominated blend solution is used. Moreover, the diameters of both the cylindrical holes and the cylinders decrease as the PT- tert-ESTER concentration is increased in the respective ranges of the PT- tert-ESTER/PMMA ratios where the patterns are formed. Grazing incident X-ray diffraction data have indicated that the patterning of the PT- tert-ESTER component in the blend films improves the crystallinity of PT- tert-ESTER as well as the molecular packing of the insoluble polythiophene in the resultant patterned polythiophene films. [ABSTRACT FROM AUTHOR]

The influence of crystallization temperature ( T ) on the number of spiral growths on poly(butylene succinate) (PBS) single crystals, obtained by self-seeding method, was systematically studied. The studies show that the statistical average number of spiral growths formed on the PBS single crystals decays exponentially with respect to the Tc. Inspired by BCF (Bruton, Cabrera and Frank) theory and L-H (Lauritzen and Hoffman) theory, a thermodynamic model has been proposed, in which the origin of spiral growth was treated as a nucleation process. The model suggests that the nucleation rate of spiral growth depends on the inverse square of super-cooling degree, which predicted the density of spiral growth formed on lamellae, and was consistent with the experiments very well. [ABSTRACT FROM AUTHOR]

The mechanical properties and phase morphologies of cis-1,4-butadiene rubber (BR) blended with polyethylene (PE) at different blend ratios were studied. The tensile test results show that the PE exhibits excellent reinforcing capabilities towards BR. Blending BR with PE results in a remarkable enhancement of tensile strength, modulus and the elongation at break simultaneously. An increment of tensile strength from 1.11 MPa to 16.26 MPa was achieved by incorporation of 40 wt% PE in the blends. The modulus and elongation at break of 40/60 PE/BR blends are also about 5 times higher than those of the pure BR treated under exactly the same conditions. The tear test indicates that the tear strength also increases with the increase of PE content. It reaches 58.38 MPa for the 40/60 PE/BR blend, which is approximately 10 times higher than that of the pure BR. Morphological study demonstrates that the PE forms elongated microdomains finely dispersed in the BR matrix when its content is over 30 wt%, which corresponds to the remarkably enhanced mechanical properties. According to the results, reinforcement mechanism of PE toward BR dependent on the microstructure has been discussed and two different mechanisms have been proposed. [ABSTRACT FROM AUTHOR]

Oriented thin films of P3HT were obtained by a friction-transfer technique. The morphology and structure of the film were studied by means of optical microscopy, atomic force microscopy and transmission electron microscopy. Optical microscopy observation indicates that large size well-ordered P3HT thin films can be produced by a friction-transfer technique. Highly ordered lamellae were observed in P3HT friction-transferred films by electron microscopy. Electron diffraction results confirm the existence of high orientation with the a- and c-axes of P3HT crystals aligned in the film plane while the c-axis parallel to the friction-transfer direction. The atomic force microscopy observation of the as-prepared P3HT thin film shows, however, a featureless top surface morphology, indicating the structure inhomogeneity of the obtained film. To get highly oriented P3HT thin films with homogenous structure, high temperature annealing, solvent vapor annealing and self-seeding recrystallization of the friction-transferred film were performed. It is confirmed that solvent vapor annealing and self-seeding recrystallization methods are efficient in improving the surface morphology and structure of the frictiontransferred P3HT thin film. Highly oriented P3HT films with unique structure can be obtained through friction-transfer with subsequent solvent vapor annealing and self-seeding recrystallization. [ABSTRACT FROM AUTHOR]

Phase structure and crystallization behavior of polyethylene (PE) in its blends with cis-1,4-butadiene rubber (BR) at different blend ratios and sample preparation conditions were studied. The PE is finely dispersed in the BR matrix. For samples hot pressed at 145 °C, circular PE microdomains with randomly oriented PE lamellar aggregates were produced. The domain size and number increase with increasing PE content. When the PE content is over 10 wt%, most of the PE domains impinged each other. The separated PE domains are connected by PE stripes with parallel arranged lamellar aggregates. For samples hot pressed at 140 °C, elongated PE microdomains with oriented PE lamellar aggregates were obtained due to the shear flow. The crystallization of PE in the blends depends on the phase structure. Confined crystallization of PE occurs in small microdomains at relatively low temperature. With the increase of domain size, the crystallization ability of PE increases while the confined crystallization decreases. [ABSTRACT FROM AUTHOR]

The intermolecular interaction between poly(vinylphenol) (PVPh) and polycaprolactone (PCL) and the crystallization behavior of PCL in PCL/PVPh blends with different compositions and under different conditions were investigated by Fourier transform infrared spectra (FTIR) and differential scanning calorimetry (DSC). It has been shown that the PCL in the blends with different blend ratios all exists in crystalline state after solution casting, even though the crystallinity decreases with increasing PVPh content. For the melt crystallized samples, PCL in its 80/20 PCL/PVPh sample can still crystallize. The crystallinity is, however, lower than that of the solution cast sample. For blends containing 50% or 20% PCL, the as-cast samples are semicrystalline and can change to compatible amorphous state after heat treatment process. FTIR analysis shows the existence of hydrogen bonding between PCL and PVPh and the fraction of hydrogen bonds increases remarkably after heat treatment process. [ABSTRACT FROM AUTHOR]

The crystallization behavior of PEOs with molecular weight of 10k and 200k as well as their blends was studied in details. The results show that the lower molecular weight PEO crystallizes with faster crystallization rate as judged from a shorter time for completing the crystallization. On the other hand, the higher molecular weight PEO crystallizes at relatively higher temperature, indicating an early start of crystallization compared with the lower molecular weight one. The blends of these two PEOs with different blend ratios always cocrystallize during the cooling processes. It is confirmed that mixing of the 10k PEO with the 200k one is in favor of the crystallization of the system. This is not only demonstrated by the early start of the crystallization at higher crystallization temperature, and also a faster crystal growth of the blend with respect to the 200k PEO. The crystallization of the blends at higher temperature is caused by an early start of nucleation and an increment of nucleus density. This may originate from the density fluctuation of the blend and a reduction in energy barrier for nucleation. Moreover, it is found that the crystallinity of the 10k PEO rich blends increases with increasing concentration of the 10k PEO. This is caused by the solvent effect of the 10k PEO toward the 200k PEO. On the other hand, the crystallinity of the 30/70 (10k/200k) PEO blend is decreased a little bit. This may be a balanced result of the improved crystallization of the 200k PEO at the expense of the high crystallization ability of the 10k PEO. [ABSTRACT FROM AUTHOR]

The crystallization behavior of poly(ethylene adipate) (PEA) on highly oriented high-density polyethylene (PE) substrate both from solution and isotropic melt was studied by means of optical microscopy, differential scanning calorimetry, atomic force microscopy and electron diffraction. The results show that the PE influences the crystallization of PEA strongly, which results in an epitaxial growth of PEA with well ordered structure. At the boundary of the PE substrate, a transcrystalline PEA layer is observed. Fine structural observation illustrates that the PEA grows on the PE substrate in edgeon lamellae with fixed orientation. Electron diffraction demonstrates that the epitaxial organization of PEA on PE occurs with both polymer chains parallel, which leads to the (00 l) PEA diffractions inclined ±23.5° to the chain direction of PE crystals. Combining the real space morphological observation and electron diffraction results, it is concluded that the epitaxial PEA edge-on lamellae are folded in the {00 l} lattice planes. [ABSTRACT FROM AUTHOR]

The dependence of properties on the structure and morphology of semicrystalline polymers offers an effective way to tailor the properties of these materials through structure control. To this end, establishing the structure and property relationship is of great importance. For a right characterization of the crystal structure, several techniques can be used. Among these techniques, electron diffraction has its advantage for determining the crystal structure related to specific formation condition since it can combine with bright and dark fields observation of the sample. This feature article describes the application of electron diffraction in determining the crystal structure of semicrystalline polymers with elaborately selected examples. We focus on how the electron diffraction can be used to disclose the crystal structure, mutual orientation of different crystals, as well as the disorders included in the polymer crystals. [ABSTRACT FROM AUTHOR]

The specular and off-specular X-ray reflectivities were efficiently employed to study the evolution of surface morphology as a function of temperature in a single layer of poly(3-hydroxybutyrate) (PHB) and a bilayer of PHB/poly(vinyl phenol) (PVPh) on Si substrates. The results indicate that the changes of thickness and surface roughness caused by pre-melting of PHB crystals are not obvious for the single layer, whereas the surface roughness of the PHB layer and the intensity of the off-specular X-ray reflectivity for the bilayer exhibit a remarkable non-monotonic change in the temperature range of 100-150°C; the roughness parameter evaluated by the specular X-ray reflectivity reaches its maximum at 120°C. The interaction at the interface between PVPh and PHB certainly contributes to the non-monotonic changes. Such interaction also affects the crystallization and melting behavior of PHB thin film greatly. The crystallization of PHB thin film is inhibited even on the glassy surface of PVPh sublayer. In the melting process, the PHB crystals on PVPh sublayer feature a three-section melting curve separated by a plateau region of 120-140°C. [ABSTRACT FROM AUTHOR]

An example of crystalline CO-based polymer from the asymmetric alternating copolymerization of CO and cyclohexene oxide is reported. Isotacticity of poly(cyclohexene carbonate) (PCHC) has the critical influence on the crystallinity, and only copolymers with a isotacticity of more than 90% are crystallizable. The stereoregular PCHC is a typical semi-crystalline thermoplastic, and possesses a high melting point ( T) of 215-230°C and a decomposition temperature of ca. 310°C. The spherulitic morphology of ( R)-PCHC grows in a clockwise spiral from a center, and that of ( S)-PCHC is a counterclockwise spiral, while the stereocomplex of ( S)-PCHC/( R)-PCHC (1/1 mass ratio) presents lath-like dendritic crystal. The novel crystalline CO-based polycarbonate represents a rare example of optically active polymers with unique crystallization behavior. Our findings reflect the critical influence of stereoregularity on the crystallization for this kind of polymeric materials, and may lead to developments of thermal-resistance CO copolymers for application in engineering thermoplastics. [ABSTRACT FROM AUTHOR]

Abstract: Crystallization and melting of a poly(ethylene oxide) (PEO) diblock copolymer containing a tablet-like block of poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene} (PMPCS) in ultrathin films have been studied using atomic force microscopy (AFM) coupled with a hot stage. The PEO and PMPCS block possess the number-average molecular weights (M n) of 5300 and 2100g/mol, respectively. The ultrathin films on the mica and glow-discharged carbon surfaces were obtained by static dilute solution casting at room temperature. Isothermal melt crystallization from ultrathin films always leads to flat-on lamellae. Selective area electron diffraction (SAED) experiments have demonstrated that the PEO blocks crystallize with a monoclinic structure identical to that of homo-PEO and the chain direction is perpendicular to the substrate. At T c<44°C, the monolayer crystals are dendrites. At T c>48°C, square-shaped crystals are formed with the (100) and (020) planes as the crystal edges. At 44°C≤T c≤48°C, an intermediate monolayer morphology is observed. The monolayer thickness increases monotonically with increasing T c. At the same T c, the monolayer lamellae with the top and bottom amorphous layers contacting with the atmosphere and the substrate possess a significantly larger overall thickness than the long period of the crystals in bulk. For the spiral terraces induced by screw dislocation, the thickness of each terrace is close to that of the monolayer formed at the same T c, and their melting is mainly determined by the terrace thickness. [Copyright &y& Elsevier]