Enthalpy Relaxation Study of Poly(Vinyl Chloride) Films Based on the Time-Temperature Superposition Principle

Abstract

In the enthalpy relaxation of poly(vinyl chloride), a decrease in enthalpy upon the isothermal ageing was measured using the differential scanning calorimetry method as a function of ageing time (t_A) and ageing temperature. The range of the ageing temperature was from 56?°C (T_g ? 25?°C) to 72?°C (T_g ? 9?°C) where T_g denotes the glass transition temperature. The limiting value of the decrease in enthalpy was determined by applying a stretched exponential function to the measured enthalpy data. The relaxation function (?) was derived from the measured enthalpy and the construction of a master curve was tried by shifting the ? ? t_A curves of the respective ageing temperatures horizontally. Although there was no agreement between the shift factors (a_T) and the relaxation times of the ? ? t_A curves, the superposition was successfully constructed and the a_T values obtained for the poly(vinyl chloride) sample were found to be comparable to those reported for viscoelastic experiments over a broad temperature range above and below T_g carried out for different polymers. The origin of the decrease in enthalpy was briefly discussed in terms of the chain dynamics in the isothermal condition.     

Swendsen‐Wang dynamics for general graphs in the tree uniqueness region

The Swendsen‐Wang (SW) dynamics is a popular Markov chain for sampling from the Gibbs distribution for the ferromagnetic Ising model on a graph G = (V,E). The dynamics is conjectured to converge to equilibrium in O(|V|^1/4) steps at any (inverse) temperature β, yet there are few results providing o(|V|) upper bounds. We prove fast convergence of the SW dynamics on general graphs in the tree uniqueness region. In particular, when β < β_c(d) where β_c(d) denotes the uniqueness/nonuniqueness threshold on infinite d‐regular trees, we prove that the relaxation time (i.e., the inverse spectral gap) of the SW dynamics is Θ(1) on any graph of maximum degree d ≥ 3. Our proof utilizes a monotone version of the SW dynamics which only updates isolated vertices. We establish that this variant of the SW dynamics has mixing time and relaxation time Θ(1) on any graph of maximum degree d for all β < β_c(d). Our proof technology can be applied to general monotone Markov chains, including for example the heat‐bath block dynamics, for which we obtain new tight mixing time bounds.     

Information percolation and cutoff for the random‐cluster model

We consider the random‐cluster model (RCM) on with parameters p∈(0,1) and q ≥ 1. This is a generalization of the standard bond percolation (with edges open independently with probability p) which is biased by a factor q raised to the number of connected components. We study the well‐known Fortuin‐Kasteleyn (FK)‐dynamics on this model where the update at an edge depends on the global geometry of the system unlike the Glauber heat‐bath dynamics for spin systems, and prove that for all small enough p (depending on the dimension) and any q>1, the FK‐dynamics exhibits the cutoff phenomenon at with a window size , where λ_∞ is the large n limit of the spectral gap of the process. Our proof extends the information percolation framework of Lubetzky and Sly to the RCM and also relies on the arguments of Blanca and Sinclair who proved a sharp mixing time bound for the planar version. A key aspect of our proof is the analysis of the effect of a sequence of dependent (across time) Bernoulli percolations extracted from the graphical construction of the dynamics, on how information propagates.     

Dielectric loss and electromagnetic absorption performance study of 1T/2H-MoS2/Mo2S3 nanocomposites with different ratios

High dielectric loss materials have an important application in electromagnetic (EM) absorption fields. In this paper, the ternary nanocomposites: 1T/2H-MoS₂/Mo₂S₃ with heterogeneous interfaces are synthesized by hydrothermal method. XRD, XPS, FTIR, SEM, and TEM measurements are applied to study the structure, morphology, and composition. The frequency spectra of complex permittivity (ε_r-f) are measured in 2–18 GHz by vector network analyzer. The results show that the nanocomposites have higher dielectric loss angle tangents than the reported 2H-MoS₂ absorbers. Based on the ε_r-f spectra, the reflection loss-frequency curves ($RL-f$) are simulated at given thicknesses. An effective absorption bandwidth of 5.2 GHz (12.8–18 GHz) and a $RL$ peak of −29.49 dB are achieved in a thin thickness of 1.62 mm, which are comparable to the reported 2H-MoS₂ absorbers with complex composition, showing that the 1T/2H-MoS₂/Mo₂S₃ nanocomposites have great application potential as an EM wave absorber in the K_u band.     

Excited State Dynamics of Isolated 6- and 8-Hydroxyquinoline Molecules

The photoinduced dynamics of isolated n-hydroxyquinoline (nHQ) molecules (n=6,8) was investigated in femtosecond pump-probe experiments. A qualitative difference was found between 8HQ and 6HQ. After an initial rapid decay corresponding to the departure of the initial wavepacket out of the Franck-Condon region of the excitation, the 8HQ probe signal decays to zero in 0.37 ps whereas a much longer time constant of 10.4 ps is observed in 6HQ. This interrogates on the role played by the intramolecular H-bond N HO which is at play the 8HQ molecule. Ab-initio were performed at the MCSCF/aug-cc-pVDZ level on the 8HQ molecule to help the discussion. A complex energy landscape was found, which includes a conical intersection.     

Macroscopic and microscopic electrical properties of a ferrofluid in a low frequency field

Using the complex dielectric permittivity measurements, in the frequency range 20 Hz – 2 MHz and at temperatures between (25–70) ^∘C, the polarizability (α), the electric modulus (M) and the electrical conductivity (σ), of a ferrofluid sample, were determined. The results enabled the computation of the thermal activation energy of electrical conduction, the obtained value being approximately equal, at 0.15 eV. By eliminating the losses arising from electrical conduction, we highlighted the existence of a Schwarz type dielectric relaxation, in the sample, at the frequency above 5 kHz. These results allowed, for the first time, the evaluation of the mechanical mobility, u, of the ions on the particle surface, resulting in a value of, $u=3.4\cdot {10}^8$ m/s N. Knowledge of macroscopic and microscopic electrical properties is useful in explaining the dielectric polarization mechanisms and relaxation processes of ferrofluids, and also in the use of ferrofluids in technological and biomedical applications.     

Progresses of Magnetic Relaxation Switch Sensor in Medical Diagnosis and Food Safety Analysis

Fast and accurate detection of complex samples in either medical diagnosis or food safety analysis are of great significance for the safeguarding of human health. Magnetic relaxation switches (MRS) technique based on superparamagnetic nanoparticles (SMP) is the combination of nano-biotechnology, nuclear magnetic resonance, chemistry and immunoassay. MRS assay has the characteristics of high sensitivity and specificity, as well as nondestructive and time-saving, and can be used in turbid complex samples. In this paper, with a brief discussion about the detection theory of superparamagnetic nanosensor, the target type, structural characteristics, limit of detection, state of magnetic nanoparticles and the change of T₂ value of MRS were reviewed. The research progresses of magnetic relaxation switch sensor in medical diagnosis of different biomarkers and the analysis of food hazard factor were also summarized. Accordingly, future research targets from three aspects, e.g., preparation and modification of magnetic nanoparticles, the improvement of detection sensitivity and construction of high flux magnetic relaxation switch sensor, were put forward.     

Finite-Volume Glauber Dynamics in a Small Magnetic Field

We consider Glauber dynamics on a finite cube in d-dimensional lattice (d2), which is associated with basic Ising model at temperature T=1/1 under a magnetic field h > 0. We prove that if the effective magnetic field is positive, then the relaxation of the Glauber dynamics in the uniform norm is exponentially fast, uniformly over the size of underlying cube. The result covers the case of the free-boundary condition with arbitrarily small positive magnetic field. This paper is a continuation of an attempt initiated earlier by Schonmann and Yoshida to shed more light on the relaxation of the finite-volume Glauber dynamics when the thermodynamic parameter (, h) is so near the phase transition line, (, h); _c < &h = 0, that the Dobrushin–Shlosman mixing condition is no longer available.     

Representations of complex hyperbolic lattices into rank 2 classical Lie groups of Hermitian type

Let Г be a torsion-free uniform lattice of SU(m, 1), m > 1. Let G be either SU(p, 2) with p ≥ 2, ${{\rm Sp}(2,\mathbb {R})}Let Г be a torsion-free uniform lattice of SU(m, 1), m > 1. Let G be either SU(p, 2) with p ≥ 2, or SO(p, 2) with p ≥ 3. The symmetric spaces associated to these G’s are the classical bounded symmetric domains of rank 2, with the exceptions of SO*(8)/U(4) and SO*(10)/U(5). Using the correspondence between representations of fundamental groups of K?hler manifolds and Higgs bundles we study representations of the lattice Г into G. We prove that the Toledo invariant associated to such a representation satisfies a Milnor-Wood type inequality and that in case of equality necessarily G = SU(p, 2) with p ≥ 2m and the representation is reductive, faithful, discrete, and stabilizes a copy of complex hyperbolic space (of maximal possible induced holomorphic sectional curvature) holomorphically and totally geodesically embedded in the Hermitian symmetric space SU(p, 2)/S(U(p) × U(2)), on which it acts cocompactly.     

On the Homological Dimension of Lattices

Let L be a finite lattice and let . It is shown that if the order complex satisfies then |L| ≥ 2 ^k . Equality |L| = 2 ^k holds iff L is isomorphic to the Boolean lattice {0,1} ^k . Research supported by the Israel Science Foundation.