Rheological Behavior of Blends of Poly(Phenylene Sulfide) with a Thermotropic Liquid Crystalline Aromatic Poly(Ether Ester)

A new type of thermotropic liquid crystalline aromatic poly(ether ester) (PEE) was prepared from 1,3-bis(4′-carboxyphenoxy)benzene, 1,4-diacetoxybenzene, and p-acetoxybenzoic acid through a melt transesterification process. The rheological behavior of blends of poly(phenylene sulfide) (PPS) with PEE was studied using a high-pressure capillary rheometer with the shear rate range of 50 s^?1 to 3000 s^?1. The results show that according to the range of shear rate, the flow curves of PEE/PPS blends can be divided into three zones: a first shear-thinning zone (n < 1, “n” represents non-Newtonian indexes), a shear-thickening zone (n > 1), and a second shear-thinning zone (n < 1), and the former two zones are more obvious with the increase of PEE content or elevated temperature. In the second shear-thinning zone, the PPS melt is close to a Newtonian fluid at high temperature and high shear rate; meanwhile the non-Newtonian behavior of the PPS melt at high temperature is enhanced with the addition of PEE. The apparent viscosity of PPS melts sharply dropped after adding PEE, especially at relatively low temperature and low shear rate. The curve of apparent viscosity vs. shear rate starts to flatten out after adding PEE, suggesting that the addition of PEE lowers the sensitivity of PPS to shear rate. As the content of PEE increases, the activation energy of the viscous flow, ΔE_η, of PPS decreases, which means that adding PEE weakens the temperature sensitivity of the apparent viscosity of the PPS melt. It can clearly be seen that the addition of PEE is beneficial to the processing of PPS.     

Shear‐Enhanced Nucleation of Isotactic Polypropylene in Limited Space

The nucleation rate was measured by directly counting the number of nuclei, which were developed while an isotactic polypropylene melt was flowing under shear in a thin film. The nucleation rate was enhanced with an increased rate of shear, e.g., by a factor of 10 larger at the rate of shear of 14 s^?1 compared with the quiescent state, at 134°C. The ratio of the shear‐enhanced nucleation rate to the nucleation rate in the quiescent state was larger at a higher temperature of crystallization, i.e., about 10 times at 134°C to 590 times at 140°C. The increase of the nucleation rate under shear flow was explained by a reduction of the lateral and end (fold) surface free energies; the product σ _s ² σ _e decreased to 3.2×10^?7 for the sheared melt, from 6.0×10^?7 (J m^?2)³ for the isotropic state. The free energy reduction was caused by transition of the nucleus formation mode from three‐dimensional folded chain nuclei to two‐dimensional bundle nuclei, in which chains lie down on the glass substrate, aligning parallel to the flow direction.     

Influence of Shearing on Crystallization Behavior of Polyoxymethylene/Poly(Ethylene Oxide) Crystalline/Crystalline Blends

The effect of shearing on crystallization behavior of a crystalline/crystalline blend, polyoxymethylene [POM]/poly(ethylene oxide) [PEO], was investigated using polarized light microscopy connected with a CSS450 shearing hot-stage, scanning electron microscopy, differential scanning calorimetry [DSC], and x-ray diffraction [XRD]. The experimental results indicated that the shearing made POM and PEO disperse more evenly and increased the inclusion and entanglement effects between the molecular chains of POM and PEO and therefore enhanced the influence of PEO on the crystallization of POM. As a result, the blend sheared at a shear rate of 20 s^?1 for 10 min at 160°C formed shish–kebab crystals and produced more interlamellar structures compared with the formation of perforated spherulites in the unsheared blend. Moreover, a more obvious shoulder melting peak of POM appeared in the DSC heating trace and a new diffraction peak occurred at 2θ = 31.7° in the XRD pattern for the sheared POM/PEO [50/50] blend.     

Direct Observation of Crystallization of Polybutene-1 Under Low Shear Rate Flow

The isothermal crystallization process of polybutene-1 melt under shear flow was investigated with an optical microscope and a device (shear flow direct observation system, SF-DOS) newly developed by our group. The nucleation rate and growth rate of polybutene-1 were studied under slow shear rates (0–0.1 s^?1) at high crystallization temperature (102–108°C) with the SF-DOS. The nucleation remains heterogeneous. The number of nuclei after long times increased and induction time decreased by increasing the shear rate. Anisotropic and distorted spherulites were observed under shear flow, while the spherulites in the static condition were isotropic. It was clearly observed that the spherulites were rotating under shear. The average growth rates were enhanced by increasing shear rates, which acts as the main factor affecting the overall crystallization kinetics. Finally, the crystallization kinetics were analyzed on the basis of the secondary nucleation theory of Hoffman and Lauritzen. Even under very low shear rates, the product of lateral‐surface free energy σ _s and fold-surface free energy σ _e was found to be reduced as shear rate increased.     

Temperature Dependence of Hyperfine Interaction for 15N Nitroxide in a Glassy Matrix at 10–210 K

Principal ¹⁵N hyperfine interaction (hfi) values in ¹⁵N-substituted nitroxide spin probe 3-carbamoyl-2,2,5,5-tetramethyl-3-pyrrolin-1-oxyl dissolved in nematic liquid crystal 4-pentyl-4′-cyanobiphenyl (5CB) were measured in a wide temperature range of 10–210 K, for 5CB frozen to a glassy state. X-band continuous-wave electron paramagnetic resonance (CW EPR) and pulse X- and Q-band ¹⁵N electron-nuclear double resonance (ENDOR) techniques were employed. To avoid microwave saturation at low temperatures in CW EPR studies, a holmium complex Ho(Dbm)₃Bpy (where Dbm is dibenzoylmethane and Bpy is 2,2′-bipyridine) was added. X- and Q-band ¹⁵N-ENDOR data have shown that the nitroxide hfi tensor is axially symmetric. The combination of data from all techniques allowed us to obtain the temperature dependence of isotropic and anisotropic parts of the nitroxide hfi tensor. Above ~100 K, a linear dependence of the anisotropic hfi value was observed, whereas below 30 K it was found to be nearly temperature independent. Such a behavior can be interpreted using the model of restricted orientational motions (librations) of a spin probe in a glassy matrix, with quantum effects occurring at low temperature (“freezing” of the librations). The energy quantum for the libration motion estimated from the temperature dependence of hfi of the spin probe is 84 cm^?1. Low-frequency Raman spectra of 5CB were also obtained, which provided the mean vibrational frequency of 76 cm^?1 for glassy 5CB.     

Atomistic study of temperature and strain rate-dependent phase transformation behaviour of NiTi shape memory alloy under uniaxial compression

Molecular dynamics simulation was conducted to investigate the phase transformation behaviour of nickel–titanium (NiTi, 50%-50% at.%) nanopillar under uniaxial compression at loading rates varying from 3.30 × 10⁷ to 3.30 × 10⁹ s^?1 and at temperatures varying from 325 to 600 K. The phase transformation of NiTi was observed to be sensitive to loading rates and temperatures. The phase transformation stress of B2 → B19 increased with increasing temperature while it was insensitive to loading rate. The phase transformation stress of B19 → B19′ → BCO increased with increasing strain rate and decreasing temperature. In addition, reverse phase transformation was observed during compression due to the interaction between the phase transformation of B19 → B19′ → BCO and the deformation twinning/dislocation slide-induced plasticity of the BCO phase, leading to different residual crystal structures after loading. Moreover, a diagram for the phase transformation behaviour of NiTi in the simulated ranges of strain rate and temperature was obtained, from which the contrary experimental observations on the phase transformation behaviour of NiTi from the studies of Nemat-Nasser et al. (Mech. Mater. 37 (2005) p.287) and Liao et al. (J. Appl. Phys. 112 (2012) p.033515) at various strain rates could be well explained.     

Flow Characteristics of Partially Hydrolyzed Polyacrylamides during Converging into a Capillary

Partially hydrolyzed polyacrylamides (HPAMs) are the most widely used polymers in enhanced oil recovery (EOR). This study presents capillary flow measurements of three different molecular weight HPAMs in synthetic brine. Polymer solutions having similar viscoelasticity were forced to flow through a 0.23 mm (radius) stainless steel capillary to investigate their flow characteristics including mobility reduction (apparent viscosity) and mechanical stability, represented by the extent of mechanical degradation (DR). The results indicated that the apparent viscosity of the polymer solutions markedly dropped with increasing flow rate until 5 mL/min, corresponding to the shear rate of 8,730s^?1; after that a slight viscosity decrease was observed. The high-molecular-weight HPAMs (6.5 and 8.0 × 10⁶ g/mol) began to have slightly greater apparent viscosity than the low-molecular-weight HPAM (1.0×10⁶ g/mol) above the shear rate of 26,180 s^?1; this might result from the occurrence of the coil-stretch transition. All the HPAMs experienced very similar percentages of mechanical degradation (10%) at shear rates between 1750 and 8730 s^?1; however, above 8730s^?1 the high-molecular-weight HPAMs exhibited a steep increase in mechanical degradation (DR). On the other hand, in the case of the low-molecular-weight HPAM, the DR curve almost leveled off at 12%. Therefore, low-molecular-weight HPAMs are generally suggested for EOR applications. These results, we suggested, should be useful to improve the efficiency of polymer EOR by minimizing mechanical degradation.     

Effect of thermomechanical processing on microstructural evolution and deformation behaviour of polycrystalline magnesium under quasi-static and high strain rate conditions

Abstract

The effect of thermomechanical processing on microstructure evolution and room temperature flow behaviour of polycrystalline magnesium in compression at strain rates of ~10^?2 and ~10³ s^?1 was investigated. Different initial microstructures were produced by optimising rolling and annealing cycles. Prior to annealing for 1 h at 350 °C, Mg samples were processed by two different treatments such as (i) hot rolling at 350 °C and (ii) hot rolling at 350 °C plus cold rolling at room temperature. Introduction of cold working step led to an increased fraction of hard oriented grains with a marginal grain size difference in post-annealed samples. A profound effect of thermomechanical processing on strain hardening rate as well as rate-sensitive flow behaviour of Mg was observed. The influence of prior processing history and strain rate on flow behaviour of Mg was clearly reflected in terms of texture strengthening/weakening phenomena and formation of microstructural deformation bands.     

Dislocation-density-based constitutive modelling of tensile flow and work-hardening behaviour of P92 steel

The flow and work-hardening behaviour of tempered martensitic P92 steel have been investigated using phenomenological constitutive model in the temperature range 300–873 K for the strain rates ranging from 3.16 × 10^?5 to 1.26 × 10^?3 s^?1. The analysis indicated that the hybrid model reduced to Estrin–Mecking (E–M) one-internal-variable model at intermediate and high temperatures. Further, the analysis also indicated that dislocation dense martensite lath/cell boundaries and precipitates together act as effective barriers to dislocation glide in P92 steel. The flow behaviour of the steel was adequately described by the E–M approach for the range of temperatures and strain rates examined. Three distinct temperature regimes have been obtained for the variations in work-hardening parameters with respect to temperature and strain rate. Signatures of dynamic strain ageing in terms of the anomalous variations in work-hardening parameters at intermediate temperatures and the dominance of dynamic recovery at high temperatures have been observed. The evaluation of activation energy suggested that deformation is controlled by the dominance of cross-slip of dislocations at room and intermediate temperatures, and climb of dislocations at high temperatures.     

Structure,thermal behavior,and dielectric properties of new cesium hydrogen sulfate arsenate: Cs<Subscript>2</Subscript>(HSO<Subscript>4</Subscript>)(H<Subscript>2</Subscript>AsO<Subscript>4</Subscript>)

Synthesis and structural characterization by single-crystal X-ray diffraction method, thermal behavior, and electrical proprieties are given for a new compound with a superprotonic phase transition Cs₂(HSO₄)(H₂AsO₄). The title compound crystallizes in the monoclinic system with the P2₁/n space group. The structure contains zigzag chains of hydrogen-bonded anion tetrahedra that extend in the [010] direction. Each tetrahedron is additionally linked to a tetrahedron neighboring chain to give a planar structure with hydrogen-bonded sheets lying parallel to (10ī). The existence of O–H and (S/As)–O bonds in the structure at room temperature has been confirmed by IR and Raman spectroscopy in the frequency ranges 4000–400 cm^?1and 1200–50 cm^?1, respectively. Differential scanning calorimetry analysis of the superprotonic transition in Cs₂(HSO₄)(H₂AsO₄) showed that the transformation to high temperature phase occurs at 417 K by one-step process. Thermal decomposition of the product takes place at much higher temperatures, with an onset of approximately 534 K. The superprotonic transition was also studied by impedance and modulus spectroscopy techniques. The conductivity in the high temperature phase at 423 K is 1.58 × 10^?4 Ω^?1 cm^?1, and the activation energy for the proton transport is 0.28 eV. The conductivity relaxation parameters associated with the high disorder protonic conduction have been examined from analysis of the M”/M”_max spectrum measured in a wide temperature range. Transport properties of this material appear to be due to the proton hopping mechanism.     

Local instability in BaF2:Mn2+: Analysis of lattice relaxation

Abstract

The distortion undergone by BaF₂ : Mn²⁺ below 50 K is examined here through the analysis of the experimental isotropic (A_s) and anisotropic (A_p) superhyperfne constants. This quantitative analysis support that the “short” Mn²⁺-F^? distance experiences a decrement of 8(4) pm with respect to the distance R= 232(2) existing in the O_h MnF₈ ^6- complex in BaF₂ at room temperature. By contrast the “long” Mn²⁺-F^? distance becomes 250(3) pm.     

Condensation heat transfer and pressure drop characteristics of R-134a inside the flattened tubes at high mass flux and different saturation temperature

In this study, heat transfer coefficients and pressure drops of R-134a inside round and flat tubes are investigated experimentally with mass flux of 450, 550, and 650 kg m^?2 s^?1 at saturation temperatures of 35°, 40°, and 45°C. The effects of mass flux and saturation temperature on heat transfer coefficient and pressure drop are examined. The maximum enhancement factor and pressure drop penalty are obtained by flat tube (FT-2) up to 2.101 at 450 kg m^?2 s^?1 and 3.01 at 650 kg m^?2 s^?1, respectively. The correlation for flat tubes is proposed to predict the heat transfer coefficient within ±20% error.     

Plastic deformation properties of Zr–Nb–Ti–Ta–Hf high-entropy alloys

We have investigated the plastic deformation properties of single-phase Zr–Nb–Ti–Ta–Hf high-entropy alloys from room temperature (RT) up to 300 °C. Uniaxial deformation tests at a constant strain rate of 10^?4?s^?1 were performed, including incremental tests such as stress relaxations, strain-rate changes, and temperature changes in order to determine the thermodynamic activation parameters of the deformation process. The microstructure of deformed samples was characterized by transmission electron microscopy. The strength of the investigated Zr–Nb–Ti–Ta–Hf phase is not as high as the values frequently reported for high-entropy alloys in other systems. At RT we measure a flow stress of about 850 °C. We find an activation enthalpy of about 1 eV and a stress dependent activation volume between 0.5 and 2 nm³. The measurement of the activation parameters at higher temperatures is affected by structural changes evolving in the material during plastic deformation.     

Cavitation in water under tension near the freezing point

Experiments are reported on cavitation in water at an initial temperature of 0.7°C under the dynamic tension created when a compression wave interacts with a free liquid surface. It is found that the tensile strength of water increases from 20 to 50 MPa as the strain rate is varied from 1.8 × 10⁴ to 5.2 × 10⁴ s^?1. It is shown that the phase state of water obtained in experiments is in a double metastable region.     

Stages of melting of graphene model in two-dimensional space

Spontaneous melting of a perfect crystalline graphene model in 2D space is studied via molecular dynamics simulation. Model containing 10⁴ atoms interacted via long-range bond-order potential (LCBOP) is heated up from 50 to 8,450 K in order to see evolution of various thermodynamic quantities, structural characteristics and occurrence of various structural defects. We find that spontaneous melting of our graphene model in 2D space exhibits a first-order behaviour of the transition from solid 2D graphene sheet into a ring-like structure 2D liquid. Occurrence and clustering of Stone–Wales defects are the first step of melting process followed by breaking of C–C bonds, occurrence/growth of various types of vacancies and multi-membered rings. Unlike that found for melting of a 2D crystal with an isotropic bonding, these defects do not occur homogeneously throughout the system, they have a tendency to aggregate into a region and liquid phase initiates/grows from this region via tearing-like or crack-propagation-like mechanism. Spontaneous melting point of our graphene model occurs at T_m = 7,750 K. The validity of classical nucleation theory and Berezinsky–Kosterlitz–Thouless–Nelson–Halperin–Young (BKTNHY) one for the spontaneous melting of our graphene model in strictly 2D space is discussed.     

Electrochemical capacitance of porous NiO–CeO2 binary oxide synthesized via sol–gel technique for supercapacitor

Nanocrystalline NiO–CeO₂ binary oxide as a novel electrode material for ultracapacitor was synthesized via glycol assisted citrate sol–gel method. Unique cubic phases with aggregated crystalline microstructure of NiO–CeO₂ mixed oxides were examined by X-ray diffraction and transmission electron microscope. The observed electrochemical measurements further reveal the strong pseudocapacitance features of the mixed oxides at different current density. Binary oxide annealed at 500 °C shows an optimum specific capacitance (C _s ) of 305 Fg^?1 at the constant current density of 1 Ag^?1. The achieved C _s value undoubtedly certifies that in combination with NiO the structural stability and redox property of CeO₂ have been enhanced. Especially, increasing the calcination temperature binary oxide has shown well reversible redox features which confirm the high chemical and thermal stability of CeO₂ and it could be involve in the charge storage process effectively by their strong Ce³⁺/Ce⁴⁺ redox couples. Capacity retention and cyclic stability of the electrode was quite good, only ～5 % capacity fading was observed after 1,000 cycles. Moreover, binary oxide calcined at 700 °C exhibits a specific capacitance of 167 Fg^?1 at the constant current density of 1 Ag^?1 which states that presence of CeO₂ with NiO have controlled the grain growth and maintains their porous microstructure even at 700 °C. This facilitates to the redox process at both NiO and CeO₂ active surfaces at elevated temperature significantly.     

Effect of In3+ ions on the electrochemical performance of the positive electrolyte for vanadium redox flow batteries

Influence of In³⁺ ions on electrochemical performance of positive electrolyte for vanadium redox flow battery was investigated in this paper. The electrochemical activity and kinetics of V(IV)/V(V) redox couple can be enhanced by the addition of In³⁺ ions, and the optimal concentration of In³⁺ ions was found at 10 mM. At this condition, the oxidation peak current with 10 mM In³⁺ ions is 46.6 mA at a scan rate of 20 mV s^?1, larger than that of pristine electrolyte (41.8 mA), and the standard rate constant is 6.53?×?10^?5 cm s^?1, 42 % larger than that of the pristine electrolyte (4.58?×?10^?5 cm s^?1). The cell using electrolyte with 10 mM In³⁺ ions was assembled, and the charge–discharge performance was evaluated, and the average energy efficiency increases by 1.9 % compared with the pristine cell. The improved electrochemical performance may be ascribed to that In³⁺ ions change the hydration state of vanadium ions in electrolyte and promote charge transfer process.     

High-temperature phase transitions in the improper ferroelectric KIO3

The ac conductivity (σ_ac) and dielectric permittivity (?) are determined in the temperature range 300?K?T3 compound. The results indicated that the compound behaves as an improper ferroelectric and undergoes a ferroelectric phase transition from a high temperature rhombohedral phase I to a low temperature monoclinic phase II at T _c?=?(486?±?1)?K. A second structural phase transition was observed around 345?K. The conductivity varies with temperature range and for T?>?428?K intrinsic conduction prevails. Different activation energies in the different temperature regions were calculated. The frequency dependence of σ(ω) was found to follow the universal dynamic response [σ(ω)∝(ω) ^s(T)]. The thermal behaviour of the frequency exponent s(T) suggests the hopping over the barrier model rather than the quantum mechanical tunneling model for the conduction mechanism.     

Solidification of selenium melt under pressure up to 6.5 GPa

Abstract

High purity selenium samples were melted under high pressure (≤6.4 GPa) and quenched at various rates ranging from 2 K s^?1 to 500 K s^?1 and the recovered material was examined by X-ray diffraction and electron microscopy. In the entire range of pressure and cooling rate, the melt was found to solidify into a polycrystalline aggregate of the trigonal phase of selenium. The samples obtained by slow cooling of the melt at 6.4 GPa contain, in addition to crystalline phase, regions which appear to be amorphous.     

Physical and mechanical properties of C60 under high pressures and high temperatures

The physical and mechanical properties of a C₆₀ fullerene sample have been investigated under high pressure–high temperature conditions using a designer Diamond Anvil Cell. Electrical resistance measurements show evidence of C₆₀ cage collapse at 20 GPa, which leads to the formation of an insulating phase at higher pressure. Energy dispersive X-ray diffraction (EDXD) data indicated that the characteristic fcc reflections gradually decrease in intensity and eventually disappear above 28 GPa. A C₆₀ sample was laser-heated at a pressure of 35 GPa to a temperature of 1910±100 K and, subsequently, decompressed to ambient conditions. The photoluminescence spectra and the Raman spectrum of the pressure–temperature-treated sample were measured at a low temperature of 80 K. Raman peak at 1322.3 cm^?1 with full-width half-maximum of 2.9 cm^?1 was observed from the sample, which is attributed to the hexagonal diamond phase in the sample. The room temperature photoluminescence spectra showed a symmetric emission band centered in the red spectral range with a peak at 690 nm. The structural analysis of the pressure–temperature-processed C₆₀ sample using EDXD method showed strong internal structure orientation and a phase close to hexagonal diamond. Mechanical properties such as hardness and Young’s modulus were measured by nanoindentation technique and the values were found to be 90±7 and 1215±50 GPa, respectively and these values are characteristic of sp³-bonded carbon materials.