Miscibility in poly(L-lactide)- b -poly( $ \upvarepsilon$ -caprolactone) double crystalline diblock copolymers

Thermally stimulated depolarization currents, TSDC, wide-angle X-ray scattering, WAXS, differential scanning calorimetry, DSC, and polarized light optical microscopy, PLOM, have been used to examine poly(L-lactide)-b -poly( -caprolactone) diblock copolymers in a wide composition range. Both components are crystallizable and the miscibility in the amorphous phase has been determined from the behavior of the primary relaxations which are the dielectric manifestation of the glass transition, and also from the superstructural morphology revealed by PLOM and the compositional dependence of the melting points as determined by DSC. Distinct segmental mobilities in the amorphous phase which can be well resolved by TSDC are present; the mode of the slower component shifts to lower temperatures as the PCL content increases while the glass transition of neat PCL is present for all compositions. A relaxation times bimodal distribution is apparent for PCL-rich copolymers. The composition dependence of the multiple glass transitions detected in these weakly segregated copolymers are predicted by the self-concentration model for a miscible blend made of components with a large T_g contrast.     

Critical Value and Control of Complexation of Polylactide Blends Using Optical Purity

On the basis of the stereocomplex formation between poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA), the stereocomplexation-induced surface properties of enantimeric polylactide blends were inverstigated by electron spectrometer for chemical analysis (ESCA) and contact angle measurements as a function of a degree of complexation. The complexation of blends was controlled by using the stereochemical polylactides (stPLAs) with percent D repeat unit contents (optical purity) of 100, 98, 95, 90, and 85%. The PLLA-b-poly(dimethyl siloxane) (PDMS)-b-PLLA triblock copolymer, instead of PLLA was used as a surface probe material because of the high surface segregation of PDMS blocks. From ESCA measurements, the surface segregation of PDMS of PLLA-b-PDMS-b-PLLA/stPLA blends with ≤10% optical impurity was rapidly decreased with a degree of complexation. However, the uncomplexed blends >10% optical impurity showed that the surface segregation of PDMS was nearly that of PLLA-b-PDMS-b-PLLA. Similar behaviors were observed in the contact angle measurements. These results indicate that 10% optical impurity is a critical value at which the complex formation and the surface properties of the PLLA-b-PDMS-b-PLLA/stPLA blends can be controlled.     

Segment relaxation in PBT/PC and PA6/ABS blends as studied by thermally stimulated depolarization currents

The segment relaxation in two series of binary, finely dispersed poly(butylene terephthalate)/polycarbonate (PBT/PC) and polyamide-6/acrylonitrile-buta-diene-styrene (PA6/ABS) blends was studied by the method of thermally stimulated depolarization currents (TSDC) both in normal mode (global TSDC spectra) and in thermal-sampling mode (TSDC-TS). The resulting temperature dependencies and distribution functions of segment relaxation activation energy E_asr and the influence of annealing on the relaxation behavior of the mixed phases are discussed, considering the phase morphology. Common to all blends under study are lower E _asrp (the most probable value of E _asr), narrower E _asr distribution functions, and broader temperature ranges of the glass transitions in both phases of the blend compared to those of the initial components. The relationships are in good agreement with the hypothesis on the spontaneous fractionation of polymers in blends and on the breakdown of the cooperative segment mobility regions caused by the interactions between the molecular chains of different polymers. In finely dispersed small particles of the PBT-rich phase (particle diameter ≥ 0.5 μm), a degeneration of the cooperative segment (a) relaxation in a noncooperative segment (β) relaxation caused by the solution of PC molecules in PBT was detected.     

Nanostructured Thermosetting Blends of Phenolic Thermosets and Poly(ethylene oxide)‐block‐poly(propylene oxide)‐block‐poly(ethylene oxide) Triblock Copolymer

The amphiphilic triblock copolymer, poly(ethylene oxide)‐block‐poly(propylene oxide)‐block‐poly(ethylene oxide) (PEO‐b‐PPO‐b‐PEO) was incorporated into novolac resin to prepare thermosetting blends. The morphology of the thermosetting blends was investigated by means of atomic force microscopy (AFM) and small‐angle x‐ray scattering (SAXS) and the nanostructures were obtained. It was identified that the reaction‐induced phase separation occurred in the blends of phenolic thermosets with the model poly(propylene oxide) (PPO), whereas poly(ethylene oxide) (PEO) was miscible with novolac resin after and before the curing reaction. In terms of miscibility and phase behavior of the subchains of the triblock copolymer with novolac resin, it was demonstrated that the formation of nanostructures in the thermosets followed a mechanism of reaction‐induced microphase separation.     

Effect of a Novel Polymeric Coupling Agent on the Water Uptake Property and Warp Stability of Poly(vinyl chloride)/Bamboo Flour Composite

Water uptake property and warp stability of poly(vinyl chloride) (PVC)/bamboo flour composite were investigated employing a novel polymeric coupling agent, poly(styrene-co-maleic anhydride)-block-poly(styrene-co-acrylonitrile) {P[(SMA)-b-(SAN)]}. P[(SMA)-b-(SAN)] was synthesized through controlled/'living' radical polymerization (CRP) technique in an one-pot reaction and incorporated into the composite to improve the interfacial adhesion between PVC and bamboo flour. The structure of P[(SMA)-b-(SAN)] was confirmed by ¹H-NMR, FT-IR and GPC. PVC/bamboo flour composite sheets were then prepared from a single screw extruder and two-roll mill in the presence of P[(SMA)-b-(SAN)] coupling agent. As the content of the coupling agent increased, improved interfacial bonding between PVC and bamboo flour filler was observed. Water uptake property and warp stability were also improved in the presence of the coupling agent. These results suggest that the block copolymer successfully acted as a coupling agent in PVC/bamboo flour composites.     

Towards Finding The Best Existing Model for Prediction of Morphology of Ternary Polymer Blends

The goal of this study was to investigate the capability of conceptual models for correct prediction of ternary blends morphology. All existing models, including spreading coefficient, relative interfacial energy, dynamic interfacial energy (DIE), and modified DIE were employed to predict the type of morphology of the polyamide 6/poly(styrene-co-acrylonitrile)/poly(styrene-b-(ethylene-co-butylene)-b-styrene) ternary system. Various samples with different compositions were prepared and predictions of the models were compared with the experimental phase morphology of the samples based on scanning electron microscopy micrographs. Additionally, the effect of elasticity of the matrix component on the both predictions and experimental phase structures of the blends was studied. It was demonstrated that, among the available phenomenological models, the modified DIE can comprehensively represent the most correct predictions for the morphology of ternary polymer blends.     

Investigation of the mobility in poly(vinylidene fluoride) ferroelectric films with different structures

The molecular mobility in two isotropic poly(vinylidene fluoride) samples crystallized in the α phase from the melt with different crystallinities and lattice perfections has been investigated by broadband dielectric spectroscopy. It has been revealed that the local-mobility parameters are insensitive to structural features. The average relaxation times of micro-Brownian motion in the disordered phase are found to be identical in the samples under consideration, which can be associated with the localization of the mobility in the interphase layer at the crystal-amorphous phase interface. The motion in the crystal (α _c transition) has been described using the soliton mechanism of relaxation. It has been found that, as should be expected, the average relaxation time increases with an increase in the longitudinal crystal size; however, in this case, a strict quantitative correlation is absent. According to the small-angle X-ray scattering data, this is caused by different microstructures of interlamellar amorphous regions. It has been demonstrated that the samples with a higher degree of crystallinity are characterized by a larger difference in the electron densities of the crystalline and amorphous phases and a larger size of the amorphous layer. It has been assumed that an increase in the concentration of chemical defects in the interlamellar layers with a simultaneous increase in their length is responsible for the increased probability of attenuation of the solitary wave (conformational defect) in its passage between neighboring lamellar crystals.     

Study of PEO—PPO—PEO Copolymers Conformational Changes: Viscosity and Dynamic Light Scattering Measurements

The self-assembly behaviour of poly(ethylene oxide)-b-poly(propylene oxide)-b-poly (ethylene oxide) copolymers, (EO)₁₃(PO)₃₀(EO)₁₃ (Pluronic L64), and (EO)₇₀ (PO)₃₀(EO)₇₀ (Pluronic F68) in water and in p-xylene has been elucidated by using viscosity and dynamic light scattering measurements to investigate the effects of hydrophilic chains length on their conformational changes. The viscosity measurements were performed for a range of temperature varying from 27°C to 60°C and concentration from 4 to 60 mg/ml. The variation of the viscosity and the conformational changes in aqueous solution depends on the kinds of interactions and the balance between excluded volume effects and hydrophobic interactions. Some dynamic light scattering measurements were also performed at room temperature for the same range of concentration to provide more information on the micellar structures in aqueous and organic solution.     

Triblock copolyampholytes from 5-(N,N-dimethylamino)isoprene, styrene, and methacrylic acid: Synthesis and solution properties

ABC triblock copolymers of the type poly[5-(N,N-dimethylamino)isoprene]-block-polystyrene-block-poly(tert-butyl methacrylate) (AiST) were synthesized and hydrolyzed to yield poly[5-(N,N-dimethylamino)isoprene]-block-polystyrene-block-poly(methacrylic acid) (AiSA) triblock copolyampholytes. Due to a complex solubility behavior the solution properties of these materials had to be investigated in THF/water solvent mixtures. Potentiometric titrations of AiSA triblock copolyampholytes showed two inflection points with the A block being deprotonated prior to the Ai hydrochloride block thus forming a polyzwitterion at the isoelectric point (iep). The aggregation behavior was studied by dynamic light scattering (DLS) and freeze-fracture/transmission electron microscopy (TEM). Large vesicular structures with almost pH-independent radii were observed. Received 15 March 2000     

Molecular dynamics of poly(ethylene 2,6-naphthalate)-polycarbonate composite by nuclear magnetic resonance

The aim of the work was to examine molecular dynamics of a series of poly(ethylene 2,6-naphthalate)-polycarbonate blends with changing weight ratio of copolymers by off-resonance nuclear magnetic resonance technique. It was shown that this technique provides information about the correlation times of the internal motions. The spectral density function amplitudes were estimated on the basis of the dispersion of the spin-lattice relaxation time off-resonanceT _lp^off. The measurements were performed for two series of blends which had been injection moulded with and without compatibilizer. The new polymer materials were also characterized using differential scanning calorimetry. Samples obtained after injection moulding and annealing became amorphous, which indicates that a reaction of transesterification process between the two polymers occurred.     

A well-defined biodegradable 1,2,3-triazolium-functionalized PEG-<Emphasis Type="Italic">b</Emphasis>-PCL block copolymer: facile synthesis and its compatibilization for PLA/PCL blends

A novel biodegradable 1,2,3-triazolium-functionalized PEG-b-PCL copolymer (TAPEC) was synthesized by the “click” coupling of methoxypolyethylene glycol azide and α-propargyl-ω-hydroxyl-poly(ε-caprolactone), followed by the quaternization of the 1,2,3-triazole moiety with iodomethane. All the intermediates and TAPEC were characterized by ¹H NMR, FT-IR, and gel permeation chromatography (GPC). Taking advantage of the characteristics of ionic liquid and block copolymer, this ion-containing diblock copolymer is expected to be used as a novel compatibilizer in mixed biopolyester for regulating the interface and crystallization behaviors. Hence, the TAPEC was evaluated as a compatibilizer and an interface emulsifier in the blends of polylactic acid (PLA) and poly(ε-caprolactone) (PCL). Non-isothermal crystallization experimental results showed that the TAPEC with the higher amount of ε-caprolactone units induces a plasticization and nucleate effect that increased the crystallization ability of the PLA phase; meanwhile, in the PCL phase, the agminated ionic cluster acting as a nucleating agent significantly increased the crystalline of PCL.     

Direct characterization of phase behavior and compatibility in PET/HDPE polymer blends by confocal Raman mapping

Morphology, chemical distribution and domain size in poly(ethylene terephthalate)/high‐density poly(ethylene) (PET/HDPE) polymer blends of various ratios prepared with and without maleic anhydride have been analyzed with confocal Raman mapping and SEM. The ratioimage method introduced here allows us to obtain enhanced chemical images with higher contrast and reliability. Compatibility numbers (N_c) are calculated to evaluate the compatibility of the blends. The incompatible polymer blends show heterogeneous distribution with phase separation behavior, while the semicompatible blends prepared with maleic anhydride show much smaller subphase distributions with less distinct interphases. After the blending modification by maleic anhydride of only 0.5%, the viscosity status and dispersibility between PET and HDPE could be substantially improved, and the interactions that exist between the two phases have also been proved by ATR‐FT‐IR results. High‐spatial‐resolution confocal Raman mapping coupled with the ratioimage method provides a very attractive way to characterize the compatibility and phase behavior of the polymer blend through different blending methodologies. Copyright © 2006 John Wiley & Sons, Ltd.     

Formation of β-iPP in Isotactic Polypropylene/Acrylonitrile–Butadiene–Styrene Blends: Effect of Resin Type,Phase Composition,and Thermal Condition

The formation of β-iPP (β-modification of isotactic polypropylene) in the iPP/ABS (acrylonitrile–butadiene–styrene), iPP/styrene–butadiene (K resin), and iPP/styrene–acrylonitrile (SAN) blends were studied using differential scanning calorimery (DSC), wide angle X-ray diffraction (WAXD), and scanning electron microscopy (SEM). It was found that α-iPP (α-modification of isotactic polypropylene) and β-iPP can simultaneously form in the iPP/ABS blend, whereas only α-iPP exists in the iPP/K resin and iPP/SAN blend samples. The effects of phase composition and thermal conditions on the β-iPP formation in the iPP/ABS blends were also investigated. The results showed that when the ABS content was low, the ABS dispersed phase distributed in the iPP continuous phase, facilitating the growth of β-iPP, and the maximum amount of β-iPP occurred when the composition of iPP/ABS blend approached 80:20 by weight. Furthermore, it was found that the iPP/ABS blend showed an upper critical temperature T _c * at 130°C for the formation of β-iPP. When the crystallization temperature was higher than the T _c *, the β-iPP did not form. Interestingly, the iPP/ABS blend did not demonstrate the lower critical temperature T _c ** previously reported for pure iPP and its blends. Even if the crystallization temperature decreased to 90°C, there was still β-iPP generation, indicating that ABS has a strong ability to induce the β-iPP. However, the annealing experiments results revealed that annealing in the melt state could eliminate the susceptibility to β-crystallization of iPP.     

Mesostructures and properties of transparent block copolymer/silica nanocomposite monoliths

In this work, three different block copolymer/silica hybrid nanocomposite monoliths that possess mesostructured domains (hexagonal, cubic, and disordered) were prepared through the micellization of the block copolymer during the sol-gel process of a silica precursor. Transparent block copolymer/silica nanocomposite monoliths were obtained from the amphiphilic triblock copolymer poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (EO₁₀₆PO₇₀EO₁₀₆, Pluronic F127), which we used to organize the polymerizing silica networks; the ratio between the block copolymer and silica was fixed at 60:40 (wt%). Small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) were used to observe the mesostructural ordering. Temperature-dependent SAXS patterns of the cubic structured nanocomposites showed that the calcination process takes place at 210°C. The transmittances of the nanocomposite monoliths over the range of wavelengths from 400 to 800 nm was >85%. From rheological measurements at low frequency, it was found that the hexagonally structured monoliths had higher storage and loss moduli relative to the monoliths possessing cubic and disordered structures.     

Conductivities of electrolytes based on PEI-b-PEO-b-PEI triblock copolymers with lithium and copper TFSI salts

Tri block-copolymer poly(iminoethylene)-b-poly(oxyethylene)-b-poly(iminoethylene) with a poly(oxyethylene) central block (PEI-b-PEO-b-PEI) were used as a “dual” matrix for polymer electrolytes having selectivity for hard cations (Li⁺/PEO) in one phase and for soft cations (Cu²⁺/PEI) in the other. Conductivity measurements were recorded for 20:1, 12:1 and 8:1 coordinating atom (O or/and N) to cation (Li⁺, Cu²⁺) ratios, for each of the three complexes studied: PEI-b-PEO-LiTFSI-b-PEI, PEI-Cu(TFSI)₂-b-PEO-b-PEI-Cu(TFSI)₂ and PEI-Cu(TFSI)₂-b-PEO-LiTFSI-b-PEI-Cu(TFSI)₂. For either low (20 °C) or high temperature (80 °C) the highest conductivity was given by the polymer electrolyte based on Cu(TFSI)₂ with N/Cu²⁺ = 20:1 (10^− 6, respectively 2 × 10^− 4 S cm^− 1). In the present paper, the conductivity evolution is discussed in relation with the polymer structure, the type and the concentration of the salt and the thermal behavior of our systems.     

In situ polymer nanocomposites: Effect of nanoparticles on the interfacial region

Composites based on the blends of polyurethane and poly(methyl methacrylate) of various composition were synthesized in situ in the presence of various amounts of nanoparticles (fumed silica). From thermophysical measurements it was found that, during reaction, phase separation and evolution of two phases occur. The temperature transitions in the systems and their positions depend on the blend composition and on various amounts of nanoparticles. Using scanning differential calorimetry from the changing of heat capacity increments the fraction of an intermediate region between two main phases has been estimated. For the first time it was observed that in nanocomposites in the temperature region between two main relaxation transitions, there appears a third transition, which was related to the adsorption layers formed by both components at the interface of the nanoparticles. The appearance of such intermediate regions increases essentially the fraction of an interfacial region in the system.     

Microhardness Studies of the Interphase Boundary in Rubber‐Softened Glassy Polymer Blends Prepared with/without Compatibilizer

Abstract

The interphase boundary of incompatible polymer blends such as poly(methyl methacrylate) (PMMA)/natural rubber (NR) and polystyrene (PS)/NR, and of compatible blends such as PMMA/NR/epoxidized NR (ENR) and PS/NR/styrene–butadiene–styrene (SBS) block copolymer, where ENR and SBS were used as compatibilizers, was studied by means of microindentation hardness (H) and microscopy. Cast films of neat PMMA and PS, and blended films of PMMA/NR, PS/NR, PMMA/NR/ENR, and PS/NR/SBS were prepared by the solution method using a common solvent (toluene). Hardness values of 178 and 173 MPa were obtained on the surfaces of the neat PMMA and PS, respectively. After the inclusion of soft phases, the binary (incompatible) and the ternary (compatible) blend surfaces show markedly lower H‐values. Scanning electron and optical microscopy reveal a clear difference at the phase boundary of the surface of compatible (smooth boundary) and incompatible (sharp boundary) blends. The compatibilized blends were characterized by using microhardness measurements, as having the thinnest phase boundary (～30 µm), while incompatible blends were shown to present a boundary of about 60 µm. The hardness values indicate that the compatibilizer is smoothly distributed across the interface between the two blend components. Results highlight that the microindentation technique, in combination with microscopic observations, is a sensitive tool for studying the breadth and quality of the interphase boundary in non‐ or compatibilized polymer blends and other inhomogeneous materials.     

Phase transition in a chloro-elpasolite,Cs2KInCl6

Using high-purity starting materials, we synthesized a new room-temperature Cs₂KInCl₆ phase (I): monoclinic (C2/c), a = 25.484(11), b = 7.699(2) and c = 13.225(3) Å, β = 100.69(3)°. A ferroelasticparaelastic phase transition is noted at T_c = 100°C (by Thermal Analysis and X-ray, Raman-scattering, electrical permittivity versus temperature) leading to the prototype Fm3m phase(II) with a = 10.870(5) Å, quenchable when very slightly spoiled by impurities.     

Amphiphilic polysilane-methacrylate block copolymers — Formation and interesting properties —

Several polysilane block copolymers have been prepared by the newly developed method, anionic polymerization of masked disilenes. Especially amphiphilic block copolymers of poly(1,1-dimethyl-2,2-dihexyldisilene) and poly methacrylate are focused. Poly(1,1-dimethyl-2,2-dihexyldisilene)-b-poly(2-hydroxyethyl methacrylate) (PMHS-b-PHEMA) is the first example of the amphiphilic polysilane copolymer that can form micelles in polar solvents. Poly(1,1-dimethyl-2,2-dihexyldisilene)-b-poly(methacrylic acid) (PMHS-b-PMAA) is more polar than (PMHS-b-PHEMA), soluble in water to form micelles. The cross-linking reaction of (PMHS-b-PMAA) with 1,10-diaza-4,7-dioxadecane and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride afforded the first shell cross-linked micelles (SCM) of polysilane. In addition to interesting properties, SCM is indicated to be able to form hollow sphere particles (hollow shell cross-linked micelles, HSCM) by a photochemical process. Reversible encapsulation of guest molecules by SCM and HSCM is demonstrated. Finally, SCM can be used as the template for the synthesis of metal nanoparticles, which may be used as catalysts.     

Time-resolved,stress-induced,and anisotropic phase transformation of a piezoelectric polymer

We investigate the time-dependent and anisotropic phase transformation of poly (vinylidene difluoride) (PVDF) under bending. Using combined techniques of an atomic force microscope and a Fourier transform infrared spectroscope, observation of surface morphology and phase transformation in time was made. Results showed that bending stress induces the transformation of amorphous, α,β, and γ crystalline phases. Specifically, the amorphous phase was transformed into the β phase when the bending force was applied. In addition, the transformation observed was time and direction dependent. The anisotropic behavior observed brings insights into the origin of the piezoelectricity of PVDF.