Phase change behavior of polyethylene glycol in blends with cellulose

Thermodynamic properties and phase change behaviors of polyethylene glycol (PEG) in blends with cellulose (CELL) were found to be completely different than those of pure PEG. When the CELL fraction of the blend was larger than 5 wt%, PEG within the blend did not melt into a liquid state, as was the case with pure PEG, even at a temperature over 50°C above its melting point. Instead of fusion, a solid-solid phase transition was found in these PEG-CELL blends with an enthalpy as large as 100 J/g.     

Synthesis and characterization of ZnO nanoparticles using polyethylene glycol (PEG)

ZnO nanoparticles and ZnO encapsulated with polyethylene glycol (PEG) was synthesized using zinc acetate as a precursor at low temperature and characterized by different techniques. The influence of the types of solvent, synthesis parameters, and PEG encapsulation on the crystallization, the surface morphology, and the luminescent properties of ZnO nanoparticles prepared by the sol–gel process were investigated. The influence of different addition molar masses of the PEG during the synthesis on the ZnO emission peaks was systematically monitored. The crystallinity, the surface morphology, and the photoluminescence (PL) properties of ZnO depended highly on the synthesis process and PEG encapsulation. X-ray diffraction (XRD) spectra of ZnO nanoparticles show that all the peaks corresponding to the various planes of wurtzite ZnO indicate the formation of a single phase. The absorption edges of these ZnO nanoparticles are shifted by additions of the PEG polymer. The photoluminescence (PL) characterization of the ZnO nanostructures exhibited a broad emission in the visible range with maximum peak at 450 and/or 560 nm.     

高聚物正电子谱学的研究进展

简要介绍了近年来正电子谱学在聚合物微结构研究中的主要应用及进展,大量实验事实表明,正电子谱学是表征高聚物微结构的极灵敏方法。     

Miscibility studies of disc-like molecules

The total miscibility method is applied to study the recently discovered mesophases of disc-like molecules, benzene-hexa-n-alkanoates. These compounds do not form continuous solid solutions, but are totally miscible in the liquid and mesomorphic states. The virtual mesophase-isotropic transition temperature for the hexanoate compound derived from the miscibility diagram is in excellent accord with that obtained from the previously reported pressure-temperature phase diagram. With simplifying assumptions, it is possible to predict with acceptable reliability the isobaric binary phase diagrams of any two members of the series. The real and virtual mesophase-liquid transition temperatures are linear functions of the molecular weight. On the other hand, a plot of the crystal-liquid transition temperatures versus the molecular weight exhibits a minimum. Total miscibility in the mesomorphic state is not observed for two members of different discogenic series, but the existence of different mesophase types is not proved. Lyotropic mesomorphism for a disc-like mesophase is established.     

Rheological,thermal, and mechanical properties of poly(ethylene naphthalate)/poly(ethylene terephthalate) blends

Structural, Theological, thermal, and mechanical properties of blends of poly(ethylene naphthalate) (PEN) and poly(ethylene terephthalate) (PET) obtained by melt blending were investigated using capillary rheometry, differential scanning calorimetry (DSC), scanning electron microscopic (SEM) observation, tensile testing. X-ray diffraction, and ¹H nuclear magnetic resonance (NMR) measurements. The melt Theological behavior of the PEN/PET blends was very similar to that of the two parent polymers. The melt viscosity of the blends was between that of PEN and that of PET. Thermal properties and NMR measurement of the blends revealed that PEN is partially miscible with PET in the as molded blends, indicating that an interchange reaction occurs to some extent on melt processing. The blend of 50/50 PEN/PET was more difficult to crystallize compared with blends of other PEN/PET ratios. The blends, once melted during DSC measurements, almost never showed cold crystallization and subsequent melting and definitely exhibited a single glass transition temperature between those of PEN and PET during a reheating run. Improvement of the miscibility between PEN and PET with melting is mostly due to an increase in transesterification. The tensile modulus of the PEN/PET blend strands had a low value, reflecting amorphous structures of the blends, while tensile strength at the yield point increased linearly with increasing PEN content.     

Study on Phase‐Change Characteristics of PET‐PEG Copolymers

Polyethylene glycol (PEG) was selected as a phase‐change material (PCM) and the phase‐change fibers of its copolymers with polyethylene terephalate (PET), PET‐PEG, were successfully prepared by melt spinning. The PET‐PEG copolymers have solid‐solid phase change characteristics at 10–60°C without obvious liquid substance appearing, while PET/PEG blends will lose their phase‐change characteristics since the PEG of the blends may melt and leak under high temperature. By controlling the molecular weight and relavent proportion of PEG added, the phase‐change temperature range and the enthalpy can be adjusted.     

Fluorescence Investigations of “Smart” Microgel Systems

Fluorescence techniques, including lifetime, quenching, and time-resolved anisotropy measurements (TRAMS), were used to study microgel systems based upon N-isopropylacrylamide (NI-PAM) using pyrene as a fluorescent probe. These experiments have revealed that poly(N-isopropylacrylamide) (PNIPAM) nanoparticles undergo a phase transition at a lower critical solution temperature (LCST), of ca. 34°C, which involves collapse of the particles into compacted, hydrophobic spheres. A degree of control over the LCST has been achieved by copolymerization of NIPAM with varying amounts of dimethylacrylamide (DMAC). Incorporation of DMAC into the gel has the effect of changing the hydrophobic to hydrophilic balance and shifts the LCST to a higher temperature. Fluorescence methods indicate that the NIPAM/DMAC gels are of a more open, water-swollen nature above the LCST than that of their PNIPAM counterparts.     

Solution calorimetric investigation of AgCl-AgI ionic conductor composites at 298 K: observation of metastable AgI modifications

The enthalpies of solution of pure silver halides AgCl and AgI and a composite material with molar composition 0.5 AgCl-0.5 AgI were measured at 298 K in a mixture of Na₂S₂O₃ (1 M) and NH₄OH (1 M). X-ray diffraction patterns showed that the composite material contained the metastable γ-AgI phase; different mechanisms for its stabilization were discussed. The phase transition enthalpies of AgI modifications and the enthalpy of formation of the composite material were deduced from the measurements. The latter could be related to a change of interfacial enthalpies.     

The relaxational behavior of heterogeneous polymers

Stress-relaxation data are presented for two commercial grades of ABS and an ABS-polycarbonate blend over a temperature range which includes the glassy, transition, and entanglement regions. Reduced master curves and the shift factor, a_T, are obtained and compared to data for fractionated polystyrene and polycarbonate; the principle of time-temperature superposition is shown to be as applicable to the relaxation data for these heterogeneous polymers as to similar data for homogeneous polymers. Compared with homogeneous polymers, the reduced curves for the composites are different in several ways: A slightly larger negative slope in the glassy region, a more diffuse transition region, a higher and broader entanglement plateau, and a smaller negative slope in the flow region are noted. For the two ABS polymers, the temperature dependences of a_T are about that of a homogeneous polymer with an equivalent Tg, indicating that the discrete rubber particles do not alter the relative relaxational behavior of this heterogeneous system. For the ABS-polycarbonate blend (both phases continuous), the temperature dependence of a_T is close to that of the polycarbonate component. suggesting that in this case the continuous phase with the longest relaxation times dominates the relaxational behavior of the composite.     

Calorimetric study of phase transitions in nanocomposites of quantum dots and a liquid crystal

The complex specific heat is measured over a wide temperature range for the liquid crystal (LC) 4-cyano-4-octylbiphenyl (8CB) and cadmium sulfate quantum dots (QDs) composites as a function of QD concentration. The thermal scans were performed under near-equilibrium conditions for all samples having QDs weight percent (φ_w) from 0 to 3wt% over a wide range of temperature well above and below the two transitions in pure 8CB. Isotropic (I) to nematic (N) and nematic to smectic-A (SmA) phase transitions evolve in character and their transition temperatures offset by (～2.3 to 2.6 K) lower for all composite samples as compared to that in pure 8CB. The enthalpy change associated with I–N phase transitions shows slightly different behavior on heating and cooling and it also shows crossover behavior at lower and higher QD content. The enthalpy change associated with N–SmA phase transitions is independent of QD loading and thermal treatment. Given the homogeneous and random distribution of QD in these nanocomposites, we interpret that these results as arising that the nematic phase imposes self-assembly on QDs to form one-dimensional arrays leading to QDs and induces net local disordering effect in LC media.     

Thermal and Mechanical Properties of Poly(lactic acid)/Modified Carbon Black Composite

Poly(ethylene glycol) (PEG) was added as a plasticizer to the composite of poly(lactic acid) (PLA) and a modified carbon black (MCB). Among the three different molecular weight (M_n = 1000, 2000, 6000) PEGs used, PEG2000 promoted crystallization of PLA and enhanced the nucleation activity of MCB more efficiently than the other two. The crystallization rate of PLA/PEG2000/3 wt% MCB composite was three times that of PLA. Although a small decrease in tensile strength and modulus of elasticity of the composite was found as the PEG content increased, the elongation at break of the PLA/PEG/MCB composites significantly improved. When the PEG2000 content was 15 wt%, the elongation at break of the blend was 90%, 4.5 times that of the neat PLA.     

Effect of polymer viscosity on morphological and electro-optic properties of aligned polymer dispersed ferroelectric liquid crystal composite films

A room temperature ferroelectric liquid crystal mixture was dispersed in UV curable polymers of different viscosity in 30:70 wt/wt ratio. These polymer dispersed ferroelectric liquid crystal (PDFLC) composite films were prepared by polymerization induced phase separation technique. It was found that the polymer viscosity influences the droplet size and the electro-optic properties. The spontaneous polarization of PDFLC decreases with an increase in polymer viscosity. The droplet morphology and electro-optic properties of these materials have been investigated in an aligned configuration.     

Morphology,conductivity, and mechanical properties of polypyrrole-containing composites

An electrical-conducting polypropylene/polypyrrole (PP/PPy) composite was prepared by the chemically oxidative modification reaction of pyrrole on the surface of PP particles in suspension. Another type of PP/PPy composite was prepared by mixing the coated PP particles with noncoated PP particles at room temperature. The composites were processed by compression molding or by injection molding. The injection-molded composites exhibited better mechanical properties compared to compression-molded samples, while these composites showed better antistatic behavior and electrical conductivity. The differences in the behavior of the two types of composites were caused by the different structure of the PPy phase, which was studied by hot-stage optical microscopy and X-ray photoelectron spectroscopy (XPS).     

Preparation and Characterization of New Biodegradable Films Made from Poly(L-Lactic Acid) and Chitosan Blends Using a Common Solvent

Poly-(L-lactic acid) (PLLA) has been widely used for various biomedical applications due to its interesting properties such as its mechanical behavior, processability, biocompatibility, and biodegradability. Blending this polymer with chitosan that, besides being biodegradable and hydrophilic, can interact with anionic glycosaminoglycans, proteoglycans, and other negatively charged molecules of the extracellular matrix, could constitute an excellent way to improve the biological performance of PLLA in these kinds of applications. Such blends could also be used in environmental applications. In this work a new and simple method of preparing biodegradable blends of chitosan and PLLA at room temperature was developed. To the best of our knowledge, this is the first time that a common solvent for the two polymers has been used, hexafluor-2-propanol (HFIP), to produce a homogeneous solution containing both PLLA and chitosan. We also anticipate that this solvent can also be used to compatibilize other combinations of natural and synthetic polymers. Membranes were then obtained by solvent casting. Films with different fractions of each component were successfully prepared and didn't show visible phase separation. The prepared films were characterized by differential scanning calorimetry (DSC) in order to analyze the miscibility of the two components as a function of the composition of the film.     

Preparation and Characterization of Novel Polyimides with Hydroxyl Groups

3,3′-diamino-4,4′-dihydroxybiphenyl (DADHBP) was synthesized and its chemical structure was confirmed by Fourier transform infrared (FT-IR) spectroscopy, ¹H-nuclear magnetic resonance (¹H-NMR), and differential scanning calorimetry (DSC). Then six poly(amic acid) (PAA) solutions were prepared by copolymerization of DADHBP, oxydiphthalicanhydride (ODPA), and 2,2-bis [4-(4-aminophenoxy)phenyl] propane (BAPOPP) in N,N-dimethylacetamide (DMAC) in different mole ratios. The polyimide (PI) films were obtained through thermal imidazation reactions of the thin layers of the above-mentioned precursor solutions. Chemical structures of all PI films were demonstrated by FT-IR. Thermal stabilities and decomposition behaviors of the PI films were tested by DSC and thermogravimetric analysis (TGA). Thermal measurements indicate that the polymers have high thermal stability and produce high char yields. The properties of the PI films were further studied by ultraviolet–visible spectroscopy, water absorption, surface energy, and mechanical measurements. Thermal analysis showed glass transition temperatures between 205.9°C and 276.7°C. Decomposition temperatures were higher than 360.2°C, with 10% weight losses in the range of 448.6°C～517.8°C. The prepared PI films also exhibited good UV absorption, low water absorption (<2%), low surface energy (<44.28 mJ/m²), and good mechanical properties.     

纳米石墨烯片-正十八烷复合相变材料制备及热物性研究

本文分别制备了纳米石墨烯片质量分数为0%, 0.5%, 1%, 1.5%, 2%的纳米石墨烯片-正十八烷复合相变材料,并通过扫描电镜测试、红外光谱分析、差示扫描量热实验及导热分析等实验对其形貌结构及热物性进行表征和研究.实验表明本文制备的纳米石墨烯-正十八烷复合相变材料具有很好的相变稳定性;当纳米石墨烯片的质量分数达到2%时,复合相变材料的导热系数相对于纯十八烷高出了89.4%.     

Viscosity,Ultrasonic, and Refractometric Studies of Chitosan/Polyethylene Glycol Blend in Solution at 30, 40, and 50°C

Measurements of viscosity, ultrasonic velocity, refractive index, and density of chitosan (CS)/polyethylene glycol (PEG) blends in buffer solution (0.1 M acetic acid+0.2 M sodium acetate) were carried out for different blend compositions at 30, 40, and 50°C. Using the viscosity data, interaction parameters μ and α were computed to determine miscibility. These values revealed that the blend was miscible when the chitosan content was more than 60% of the blend. The results were further confirmed by ultrasonic velocity, density, and refractive index measurements. Further, the results revealed that the change in temperature has no significant effect on the miscibility of CS/PEG polymer blends.     

Morphology and infrared spectroscopy of strongly interacting polymer blends: EVOH/copolyamide-6/6.9

The presence of aliphatic hydroxyl groups in poly(ethylene-co-vinylaleohol) (EVOH) suggests that these copolymers have the potential of forming miscible blends, within certain composition ranges, with a variety of polymers containing complementary functional groups. Hydrogen bonding in EVOH involves a wide variety of inter- and intramolecular species and plays an important role in the phase behavior of EVOH blends. Polymer blends of two random copolymers, EVOH with different ethylene contents and copolyamide-6/6.9 (COPA) at an approximately 1:1 comonomer ratio, were investigated using Fourier transform infrared (FTIR), near-IR, transmission electron microscopy (TEM), and scanning electron microscopy (SEM) methods. The blends were found to be partially miscible due to intermolecular hydrogen bonding between the OH group of the EVOH and the amide group of the copolyamide. The EVOH-rich blends exhibit much lower miscibility compared with the copolyamide-rich blends.     

Effect of hydrostatic pressure on closed-loop phase behavior of block copolymers

The effect of hydrostatic pressure (P) on closed-loop phase behavior of deuterated polystyrene-block-poly(n-pentyl methacrylate) copolymers [dPS-PnPMA] was investigated by using small-angle neutron scattering and birefringence. For P<20.7 bar, dPS-PnPMA exhibited a lower disorder-to-order transition temperature (T(LDOT)) at 175 degrees C, and then an upper order-to-disorder transition temperature (T(UODT)) at 255 degrees C. With increasing pressure both T(LDOT) and T(UODT) were markedly changed, where dT(LDOT)/dP was 725 degrees C/kbar and dT(UODT)/dP was -725 degrees C/kbar. These are consistent with predictions by the Clausius-Clapeyron equation using measured values of the volume and enthalpy changes of both transitions. The large pressure coefficients imply that the closed-loop phase behavior observed for PS-PnPMA is an entropic-driven phase transition.     

Gel–liquid crystal phase transition in dry and hydrated SOPC phospholipid studied by differential scanning calorimetry

We study the thermodynamic properties of pure and hydrated samples of SOPC (stearoyl-2-oleoyl-sn-glycero-3-phosphocholine) membrane via Differential Scanning Calorimetry. We estimate the fundamental thermodynamic quantities, such as enthalpy and entropy, of the bilayer phosphatidylcholine. It is found that the gel-liquid crystal phase transition is driven by the van’t Hoff enthalpy, revealing the occurrence of an intermediate phase transition. We discuss the influence of the heating rate on the enthalpy and on the gel ? liquid crystal phase transition temperature by introducing the adequate thermodynamic Gibbs potential. The effect of hydrogen bonding of the water molecules with the polar head and polar-apolar interface on the energetics of the bilayer membrane matrix is analysed. The obtained transition temperature was found to vary between 3 and 4°C depending on the hydration level. A result corroborated by the behaviour of the heat capacity of SOPC computed via Molecular dynamics simulation.