The crystalline morphology formed in binary blends of poly(ε-caprolactone)- block-polyethylene (PCL-b-PE) copolymers and PCL homopolymers has been examined using synchrotron small-angle X-ray scattering (SR-SAXS) and differential scanning calorimetry (DSC) as a function of the homopolymer fraction in the blend. The PE block crystallized first on quenching from a lamellar microdomain structure to set a hard lamellar morphology (PE lamellar morphology) in the blend, followed by the crystallization of PCL chains (i.e., PCL homopolymers + PCL blocks). Two binary blends were studied by considering the miscible state of PCL homopolymers in the microdomain structure: when the PCL homopolymers were uniformly mixed with PCL blocks, they formed a mixed crystal. When the PCL homopolymers were localized between PCL blocks in the microdomain structure, DSC results suggested the possible formation of separate PCL crystals in the PE lamellar morphology. The effect of the advance crystallization of PE blocks on the subsequent crystallization of PCL chains was discussed as compared with the crystalline morphology formed in PCL-block-polybutadiene copolymer/PCL homopolymer blends, where the crystallization of PCL chains started directly from a microdomain structure without forming the hard lamellar morphology. 相似文献
Morphology and deformation behavior of binary blends comprising styrene/butadiene block copolymers (polystyrene content, ΦPS∼0.70) having different molecular architectures were studied by means of transmission electron microscopy and tensile testing. In contrast to the binary diblock copolymer blends discussed in literature, the phase separation behavior of the blends investigated was found to be strongly affected by asymmetric molecular architecture. The blends showed macrophase separated grains, in which the structures resembled the microphase morphology of none of the blend components. Unlike the classical rubber-modified or particle-filled thermoplastics, neither debonding at the particle/matrix interface nor the particle cavitation was observed in these nanostructured blends. The microdeformation of the blends revealed plastic drawing of polystyrene lamellae or PS struts dispersed in rubbery matrix and orientation of the whole deformation structures along the strain direction. 相似文献
The influence of morphology on micromechanical deformation behaviour of blends consisting of a lamellar forming styrene/butadiene star block copolymer and polystyrene homopolymer (hPS) was studied by transmission electron microscopy (TEM). The pure star block copolymer and the microphase separated blends revealing lamellar structure with polystyrene (PS) lamella thickness in the range of about 20 nm showed homogeneous plastic deformation of the PS lamellae. The macrophase separated blends with PS particles in lamellar matrix exhibited debonding at the particle–matrix interface associated with extensive plastic deformation of the surrounding matrix. The blends containing PS matrix deformed via crazing. 相似文献
The temperature-composition phase diagrams for six pairs of diblock copolymer and homopolymer are presented, putting emphasis on the effects of block copolymer composition and the molecular weight of added homopolymers. For the study, two polystyrene-block-polyisoprene (SI diblock) copolymers having lamellar or spherical microdomains, a polystyrene-block-polybutadiene (SB diblock) copolymer having lamellar microdomains, and a series of polystyrene (PS), polyisoprene (PI), and polybutadiene (PB) were used to prepare SI/PS, SI/PI, SB/PS, and SB/PB binary blends, via solvent casting, over a wide range of compositions. The shape of temperature-composition phase diagram of block copolymer/homopolymer blend is greatly affected by a small change in the ratio of the molecular weight of added homopolymer to the molecular weight of corresponding block (MH,A/MC,A or MH,B/MC,B) when the block copolymer is highly asymmetric in composition but only moderately even for a large change in MH,A/MC,A ratio when the block copolymer is symmetric or nearly symmetric in composition. The boundary between the mesophase (M1) of block copolymer and the homogeneous phase (H) of block copolymer/homopolymer blend was determined using oscillatory shear rheometry, and the boundary between the homogeneous phase (H) and two-phase liquid mixture (L1+L2) with L1 being disordered block copolymer and L2 being macrophase-separated homopolymer was determined using cloud point measurement. It is found that the addition of PI to a lamella-forming SI diblock copolymer or the addition of PB to a lamella-forming SB diblock copolymer gives rise to disordered micelles (DM) having no long-range order, while the addition of PS to a lamella-forming SB diblock copolymer retains lamellar microdomain structure until microdomains disappear completely. Thus, the phase diagram of SI/PI or SB/PB blends looks more complicated than that of SI/PS or SB/PS blends. 相似文献
The isothermal crystallization kinetics and morphology have been investigated for a series of dilute binary blends using six monodisperse n-alkanes as guest in C162H326 as host. Two patterns of behaviour were observed. Guest molecules shorter than the host segregate as a separate population causing growth rates to become both reduced and non-linear. Morphologies are then noticeably less spherulitic than the host with less divergence between adjacent dominant lamellae but exhibiting no additional splaying at zero supercooling. By contrast, those blends with an n-alkane longer than the host co-crystallize (producing permanent cilia of controlled length) with a constant, but reduced, isothermal lamellar growth rate. Textures are now more spherulitic than the host, with additional splaying of an amount directly proportional to the number of permanent cilia and increasing with their length. The intercepts and slopes of plots of splaying data against supercooling are consistently related to permanent cilia plus inclined packing of initially rough lamellar surfaces and transient ciliation, respectively. The underlying causes of spherulitic growth for long molecules are thereby further confirmed and clarified. 相似文献
The crack toughness behaviour of styrene/butadiene block copolymers of triblock and star architectures was investigated using instrumented Charpy impact testing. In order to evaluate adequately the toughness behaviour of the investigated materials, different concepts of elastic‐plastic mechanics (J‐integral and crack‐tip opening displacement, CTOD concepts) were used. Although the lamellar block copolymers showed a remarkably enhanced ductility in the tensile test than the neat block copolymer having hexagonal PB cylinders in PS matrix, no pronounced difference in crack toughness was found. This behaviour implies that the tensile strain cannot be regarded as the only parameter defining the toughness value. A brittle/tough transition was observed in a lamellar star block copolymer on blending with a linear thermoplastic elastomeric SBS triblock copolymer.
SEM micrograph showing the details of the stable crack propagation region in a binary block copolymer blend. 相似文献
The micromechanical properties (microindentation hardness, H, elastic modulus, E) of poly(ethylene terephthalate) (PET), isothermally crystallized at various temperatures (Ta) from the glassy state are determined to establish correlations with thermal properties and nanostructure. Analysis of melting temperature and crystal thickness derived from the interface distribution function analysis of SAXS data reveals that for Ta<190 °C the occurrence of two lamellar stack populations prevails whereas for samples annealed at Ta>190 °C a population of lamellar stacks with a unimodal thickness distribution emerges. The H and E-values exhibit a tendency to increase with the degree of crystallinity. The results support a correlation E/H∼20 in accordance with other previously reported data. The changes of microhardness with annealing temperature are discussed in terms of the crystallinity and crystalline lamellar thickness variation. Unusually high hardness values obtained for PET samples crystallized at Ta=190 °C are discussed in terms of the role of the rigid amorphous phase which offers for the hardness of amorphous layers constrained between lamellar stacks a value of Ha∼150 MPa. On the other hand, for Ta=240 °C the decreasing H-tendency could be connected with the chemical degradation of the material at high temperature. 相似文献
Fracture behavior of binary blends comprising of styrene-butadiene block copolymers having star and triblock architectures was studied via instrumented Charpy impact test. The toughness of the ductile blends was characterized by dynamic crack resistance curves (R-curves).This study represents a systematic investigation of crack resistance behavior of nanometer structured binary block copolymer blends and the development of a new material with a combination of high toughness and transparency, usually not observed in incompatible polymer blends. While the lamellar star block copolymer shows an elastic behavior (small-scale yielding and unstable crack growth), adding of 20 wt% of the triblock copolymer leads to a stable crack growth and at 60 wt% of the triblock copolymer the strong increase of toughness values indicate a tough/high-impact transition, demonstrating the existence of novel toughening concepts for polymers based on nanometer structured materials. 相似文献
Crystallization of two oxyethylene/oxybutylene block copolymers (E76B38 and E155B76) from micelles in block copolymer/amorphous homopolymer blends was studied by differential scanning calorimetry (DSC) and time-resolved small angle X-ray scattering (SAXS). Unlike the simultaneous crystallization and formation of superstructure in crystallization from an ordered structure, crystallization of block copolymer from micelles can be divided into two steps. The core of the micelles firstly crystallizes individually, with first-order crystallization kinetics and homogeneous nucleation mechanism. The SAXS revealed that crystallization-induced deformation occurs for the micelles, which strongly depends on microstructure of the block copolymers. For the shorter block copolymer E76B38, larger deformation induced by crystallization was observed, leading to coalescence of the micelles after crystallization, while for the longer block copolymer E155B76 the micelles show little deformation and the morphology of micelle is retained after crystallization. 相似文献
We report the morphological characterization of asymmetric miktoarm star block copolymers of the (PS-b-PI)nPS type where n=2,3 (denoted 2DB and 3DB miktoarm stars, respectively) and a symmetric super H-shaped block copolymer of the (PS-b-PI)3PS(PI-b-PS)3 type (denoted SH) which were synthesized by anionic polymerization. The initial volume fraction of PS (φPS) for each copolymer was 0.51-0.56, giving a lamellar morphology. Addition of homopolystyrene (hPS) with a molecular weight lower than the respective PS blocks in the neat materials lead to a transition from the lamellar structure to hexagonally packed cylinders. Addition of low molecular weight homopolyisoprene (hPI) on the other hand, only resulted in swollen lamellae even when the overall composition was highly asymmetric (80/20). Changes in the lamellar spacing as well as in the respective PS and PI layer thickness were measured by SAXS. The transition from lamellae to cylinders with increased PS content occurred without the observation of an intervening cubic morphology for the 2DB and 3DB miktoarm stars. However, blends with 30 and 35% hPS ((φPS)total=0.68-0.70) with the super H-shaped block copolymer lead to the observation of lamellar-catenoid structures. 相似文献
The morphology of a melt-quenched crystalline-crystalline diblock copolymer, poly(ε-caprolactone)-block-polyethylene (PCL-b-PE), was studied by small-angle X-ray scattering and transmission electron microscopy. The melting behavior of PCL-b-PE was also investigated by differential scanning calorimetry. The melting temperature of PCL blocks, Tm,PCL, was ca. 55 °C and that of PE blocks was ca. 96 °C. Therefore, the PE block always crystallized first during quenching from the microphase-separated melt into various temperatures Tc below Tm,PCL to yield an alternating structure composed of PE lamellae and amorphous layers (PE lamellar morphology), and subsequently the crystallization of PCL blocks started at Tc after some induction period. The PE lamellar morphology was preserved after the crystallization of PCL blocks at low crystallization temperatures (Tc<30 °C), that is, the PCL block crystallized within the PE lamellar morphology. At high crystallization temperatures (45 °C>Tc>30 °C), on the other hand, the crystallization of PCL blocks destroyed the PE lamellar morphology to result in a new lamellar morphology mainly consisting of PCL lamellae and amorphous layers (PCL lamellar morphology). The PE crystals were fragmentarily dispersed in the PCL lamellar morphology. 相似文献
This work examines the effect of microstructure (aspect ratio of mullite crystals and proportion of crystalline and amorphous phases) as well as different physical features (bulk density, closed and open porosity and absolute density) on the mechanical properties of a standard porcelain stoneware composition (50% kaolinitic clay, 40% feldspar and 10% quartz) fired in the 1200–1300 °C temperature interval using a fast firing schedule. The mechanical behaviour was evaluated in terms of bending strength, Vickers microhardness, fracture toughness and Young's modulus. After viewing the results, it can be concluded that increased σf, Hv and E values were mainly due to open porosity, percentage of mullite phase and morphology of secondary mullite needles, whereas closed porosity and quartz particles have no influence on these properties. 相似文献