Effects of the volume and temperature on the global and segmental dynamics in poly(propylene glycol) and 1,4‐polyisoprene

Published dielectric relaxation measurements for poly(propylene glycol) and 1,4‐polyisoprene are analyzed to determine the relative effects that thermal energy and volume have on the temperature dependence of the normal‐mode relaxation times, and these are compared with their effects on the temperature dependence of the local segmental relaxation times. For both polymers at temperatures well above the glass‐transition temperature, both relaxation modes are governed more by the thermal energy than by the volume, although the latter's contribution is not negligible. Such a result is consistent with an assumption underlying models for polymer viscoelasticity, such as the Rouse and tube models, that the friction coefficient governing motions over large length scales can be identified with the local segmental friction coefficient. Moreover, the relaxation data for both the segmental and normal modes superimpose when expressed as a function of the product of the temperature and volume, the latter being raised to a power. This scaling form arises from an inverse power law for the repulsive part of the intermolecular potential. The value of the exponent on the volume is the same for the normal and segmental motions and for both polymers indicates a relatively soft potential. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4313–4319, 2004     

Anomalous rheology in a nanostructured diblock copolymer/hydrocarbon system and its kinetic origin

Nanostructured squalane solutions (5–20 wt %) of a diblock copolymer, poly(styrene‐b‐hydrogenated isoprene), were prepared by a cosolvent‐casting method. The as‐cast solutions behaved as viscous liquids with terminal flow behavior at room temperature. Upon heating, the solutions gelled, and they did not return to their starting liquidlike state upon cooling. Small‐angle X‐ray scattering (SAXS) revealed a random array of spherical micelles in the as‐cast solutions, which were hypothesized to be in a nonequilibrium state. This abnormal solidification with increasing temperature was correlated with the formation of body‐centered‐cubic (BCC) structures. Isothermal SAXS and rheology measurements also indicated that the rate of formation of BCC structures in the as‐cast solutions increased with temperature. A diffusion‐controlled nucleation‐and‐growth mechanism was proposed for the ordering process in the as‐cast polystyrene‐b‐hydrogenated polyisoprene/squalane solutions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1496–1505, 2004     

Effect of silver nanoparticles on the dynamic crystallization behavior of nylon‐6

The effect of introducing silver nanoparticles on the rheological properties and dynamic crystallization behavior of nylon‐6 was investigated. The nanocomposites showed slightly higher viscosity than pure nylon‐6 in the low‐frequency range even at an extremely low loading level of the silver particles (0.5–1.0 wt %). The nanoparticles had a more noticeable effect on the storage modulus than on the loss modulus of a nylon‐6 melt and reduced its loss tangent. They increased the crystallization temperature of nylon‐6 by about 14 °C and produced a sharper crystalline peak. The silver nanoparticles promoted the crystallization of nylon‐6, and their effect on the dynamic crystallization of nylon‐6 at 200 °C was more notable at a lower shear rate and at 190 °C at a higher frequency. Nylon‐6 produced large spherulitic crystals, but the nanocomposites showed a grainy structure. In addition, the silver nanoparticles reduced the fraction of the α‐form crystal but increased that of the γ‐form crystal. The nanocomposites crystallized at 190 °C showed a lower melting temperature than nylon‐6 by about 3 °C, whereas the nanocomposites crystallized at 200 °C showed almost the same melting temperature. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 790–799, 2004     

Temporal scaling analysis: Linear and crosslinked polymers

An ansatz that predicts the frequency dependence of viscoelastic moduli of polymer solutions was tested against literature data on linear polymers and polymer microgels. Excellent agreement was uniformly found between the ansatz and the experiment. The ansatz does not give a simple reduction scheme or a master plot; it systematizes large amounts of data to a few parameters. The dependence of these parameters on polymer concentration and solvent quality was examined. The ansatz satisfies Kronig–Kramer's relations; transformations of G′(ω) and G″(ω) for a given system lead to the same G(t). © 2002 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 375–386, 2002; DOI 10.1002/polb.10099     

Molecular and structural analysis of a triepoxide‐modified poly(ethylene terephthalate) from rheological data

The effects of reactive melt modification of poly(ethylene terephthalate) (PET) with a multifunctional epoxide—triglycidyl isocyanurate—that lead to chain extension/branching and formation of gel‐like structures were rheologically characterized. The storage and loss moduli and the complex viscosity of the modified PET were larger than those of the unmodified PET. The elastic or solidlike behavior of PET was enhanced after reactive modification as a result of chain extension/branching. Modified Cole–Cole plots revealed that the modified resins show higher elasticity than the unmodified one. Reactive modification characterized by the presence of long‐chain branching resulted in a wider molecular weight distribution. The effects of mixing temperature and the concentration of modifier corresponding to different stoichiometries were investigated. Higher amounts of modifier resulted in a polymeric structure near the sol–gel transition point whose linear viscoelastic properties obey scaling law. The relaxation spectrum was calculated from the oscillatory shear data by Tschoegl equations. Certain modified resins have rheological properties suitable for process operations such as extrusion foaming, blow molding, and thermoforming. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 958–969, 2003     

Structural and rheological properties of hydrophobically modified alkali‐soluble emulsion solutions

Scattering and rheological experiments were carried out on hydrophobically modified alkali‐soluble emulsion solutions at pH ～ 7.3 as a function of the polymer concentration. The light scattering experiments revealed the existence of a liquidlike order for concentrations below approximately 0.1 × 10^?2g cm^?3 corresponding approximately to the close packing of microgels particles. Above this concentration, the zero‐shear viscosity rose sharply, whereas the ordering disappeared progressively. The results are discussed within the framework of gelation models of associating polymers. Diffusing wave spectroscopy experiments provided estimates of the high‐frequency modulus. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1985–1994, 2002     

The bordoni peak in silver single crystals at megahertz frequencies

Summary The dislocation relaxation maximum has been investigated at frequencies of 5, 10 and 30 MHz. The three (very high-purity) silver crystals of crystallographic orientation 〈111〉, 〈110〉 and 〈100〉 which are given a resolved shear stress of 20 MPa were found to produce dislocation relaxation maximum at 107 K in all the three samples. The maximum shifts to 117 K when measurement is carried out at 10 MHz and to 127 K at 30 MHz. The results reveal that the maximum is orientation independent. The activation energy and the attempt frequency were calculated and found to be equal to 0.105 eV and 2·10⁹ Hz, respectively. Meanwhile the larger magnitude of the maximum was found on the 〈111〉 crystal and the least was on the 〈100〉 crystal. Finally, it was clearly shown that the dislocation relaxation strength decreases as the frequency increases.     

高速显微摄影在金属切削、气液双相流等研究领域的应用

高速显微技术是一种在多学科中有着广泛应用潜力的研究手段。作者将高速显微摄影技术实际应用于金属切削、血液流变、气液双相流、液体气穴形成、高压玻壳汞继电器触点测量等研究领域,为这些研究领域提供了有价值的实验数据。文中分别介绍这些应用的实验情况,并给出了部分实验结果。     

The effect of neutron and gamma irradiation on the dislocation relaxation peak in silver

Summary The internal-friction spectrum has been determined in extremely pure polycrystalline silver crystals after being subjected to neutron and gamma irradiation. The spectra obtained for an applied frequency of 10 MHz show that the mechanical losses due to dislocation relaxation decrease as the doses of neutron and gamma radiation increase. The effect of gamma radiation was found to be more significant than that of neutron irradiation. The relationship between damping neutron and gamma dose was found to be of the formQ _max ⁻¹ α ΛD ^η, where η is equal to −1.2 for neutron and −1.45 for gamma irradiation. The variations of the peak height and width, and temperature of the dislocation relaxation peak as functions of neutron and gamma doses are explained in terms of the pair-kink formation model.     

Study on the thixotropy of aluminum magnesium hydroxide– Na-montmorillonite suspension

 In this paper, the thixotropy of the aqueous suspension consisting of aluminum magnesium hydroxide (AMH) possessing permanent positive charges and Na-montmorillonite possessing permanent negative charges was studied. Besides positive thixotropy and negative thixotropy, a novel thixotropic phenomenon was found, i.e., a given system studied may display, early and late, positive M28.8nthixotropic character and negative thixotropic character, we describe it as “complex thixotropy”. The content of the suspension and electrolyte may influence the forms of thixotropy of the suspension studied. Received: 4 February 1997 Accepted: 15 October 1997