Hole-transporting [3,3′]bicarbazolyl-based polymers and well-defined model compounds

Polymers containing bicarbazolyl moieties in the main chain have been synthesized by the modified Ullmann coupling reaction from 9H,9′H-[3,3′]bicarbazolyl and different dihalo derivatives. The number-average molecular weights of the polymers synthesized were in the range of 2500-6200 with a molecular weight distribution of 1.6-3.1. Well-defined model compounds for the polymers have been synthesized by stepwise reactions. All these compounds have been found to form glasses with glass transition temperatures in the range of 57-119 °C as characterised by differential scanning calorimetry. The electron photoemission spectra of the compounds have been recorded and the ionisation potentials of 5.35-5.4 eV have been established. Room temperature hole drift mobility of the synthesized compounds molecularly dispersed in a polymer host range from 10⁻⁶ to 3 × 10⁻⁵ cm²/V s at an electric field of 10⁶ V/cm at the room temperature.     

Some model theory for monotone quantifiers

A generalization of the existential and universal quantifier, the monotone quantifiers, are studied. It is shown that the model theory for monotone quantifiers behaves very much like classical model theory. Completeness theorems, definability theorems and preservation theorems are given. Ultraproducts, reduced products and Back and Forth arguments are studied.This work is part of the research program of the G.N.S.A.G. group of the Italian C.N.R.     

Complexation of Ni, Cu, Zn, and Cd by DOC in some metal-impacted freshwater lakes: a comparison of approaches using electrochemical determination of free-metal-ion and labile complexes and a computer speciation model, WHAM V and VI

Complexation of Ni(II), Cu(II), Zn(II), and Cd(II) by dissolved organic carbon (DOC) in some freshwater lakes in Rouyn-Noranda, Québec, Canada, where they were impacted by effluents from a nearby copper smelter, was measured by kinetic and equilibrium methods using cathodic and anodic stripping voltammetry. The measured free-metal-ion and labile metal-complex concentrations were compared with the predictions made by a widely-used computer speciation model, the Windermere Humic Aqueous Model (WHAM): WHAM V and its improved version WHAM VI. If it is assumed that 65% of the DOC is “active”, i.e. behaving as isolated humic substances such as fulvic acid, both versions of WHAM are able to predict the labile and free-metal-ion concentrations of Ni, Zn, and Cd reasonably well; however, both underestimate the free-copper-ion concentration by one to two orders of magnitude. WHAM VI is generally better than or equal to WHAM V for successfully predicting most of the free-metal-ion concentrations. The modelled competition by Al(III) and Fe(III) in the lake surface waters showed that in most cases Cu(II) was most affected by this competition. WHAM VI predicts a larger effect from the Al(III) and Fe(III) competition than does WHAM V.     

A simple adsorption model for ionic surfactants

In the past, few theoretical attempts have been made to describe quantitatively the adsorption of ionic surfactants at liquid interfaces. Well-known adsorption isotherms due to Frumkin or Hill–de Boer cannot respond to the specific electrostatic and geometric properties of the surfactant molecules. Our approach is based on a combination of the Gouy–Chapman theory with a modified Frumkin isotherm. The modification implies that the system is free to choose an optimal head group area and an optimal arrangement of the surfactant molecules in the interface as a function of bulk concentration. Interaction energies between neighbouring adsorbed surfactant molecules and between surfactant and water molecules are taken into consideration. The minimum of the Gibbs free energy of the system is equivalent to a minimal interfacial tension. Thus, the thermodynamically stable isotherm can be obtained as the lower envelope of the family of σ versus ln c isotherms resulting from different choices of the model parameters, including the area per molecule. According to the Gibbs equation, the Γ versus ln c adsorption isotherm is obtained as the derivative of this envelope. By variation of the model parameters, the envelope of the calculated adsorption isotherms can be fitted to experimental data of the interfacial tension versus bulk concentration. A computer program is used to calculate the σ versus c and the Γ versus ln c curves as well as to fit the parameters. Received: 28 October 1999/Accepted: 8 February 2000     

Measurement and calculation of gas compressibility factor for condensate gas and natural gas under pressure up to 116 MPa

The volumetric properties of two reservoir fluid samples collected from one condensate gas well and one natural gas well were measured under four groups of temperatures, respectively, with pressure up to 116 MPa. For the two samples examined, the experimental results show that the gas compressibility factor increases with the increase of pressure. But the influence of the temperature is related to the range of the experimental pressure. It approximately decreases with the increase of temperature when the pressure is larger than (45 to 50) MPa, while there is the opposite trend when the pressure is lower than (45 to 50) MPa. The dew point pressure was also determined for the condensate gas sample, which decreases with the increase of temperature. The capabilities of four empirical correlations and a thermodynamic model based on equation of state for describing gas compressibility factor of reservoir fluids under high pressure were investigated. The comparison results show that the thermodynamic model recommended is the most suitable for fluids whatever produced from high-pressure reservoirs or conventional mild-pressure reservoirs.     

Nonlinear vertical accelerations of a floating torus in regular waves

The longitudinal motions and vertical accelerations of a floating torus as well as wave motion inside the torus are studied by model tests in regular deep-water waves. Comparisons are made with linear and partly with second-order potential-flow theory for the smallest examined experimental wave height-to-wave length ratio 1/120. Reasonable agreement is obtained, in particular for the linear problem. The importance of 3D flow, hydroelasticity and strong hydrodynamic frequency dependency is documented. Experimental precision errors and bias errors, for instance, due to tank-wall interference are discussed. Numerical errors due to viscous effects are found to be secondary. Experiments show that the third and fourth harmonic accelerations of the torus matter and cannot be explained by a perturbation method with the wave steepness as a small parameter.     

A reduced simulation applied to the viscoelastic fatigue of polymers

The paper extends the use of the PGD method to viscoelastic evolution problems described by a large number of internal variables and with a large spectrum of relaxation times. The internal variables evolution is described by a set of linear differential equations that involve many time scales. The feasibility and the robustness of the method are discussed in the case of a polymer in a non-equilibrium state under creep and cyclic loading. The relationships between different time scales (loading and internal variables) are also discussed.     

Predictive control of uncertain nonlinear parabolic PDE systems using a Galerkin/neural-network-based model

In this paper, a model predictive control (MPC) scheme for a class of parabolic partial differential equation (PDE) systems with unknown nonlinearities, arising in the context of transport-reaction processes, is proposed. A spatial operator of a parabolic PDE system is characterized by a spectrum that can be partitioned into a finite slow and an infinite fast complement. In this view, first, Galerkin method is used to derive a set of finite dimensional slow ordinary differential equation (ODE) system that captures the dominant dynamics of the initial PDE system. Then, a Multilayer Neural Network (MNN) is employed to parameterize the unknown nonlinearities in the resulting finite dimensional ODE model. Finally, a Galerkin/neural-network-based ODE model is used to predict future states in the MPC algorithm. The proposed controller is applied to stabilize an unstable steady-state of the temperature profile of a catalytic rod subject to input and state constraints.     

Analysis of risk bounds in partially specified additive factor models

The study of worst case scenarios for risk measures (e.g. the Value at Risk) when the underlying risk vector (or portfolio of risks) is not completely specified is a central topic in the literature on robust risk measurement. In this paper we discuss partially specified factor models as introduced in Bernard et al. (2017) in more detail for the class of additive factor models which admit more explicit results. These results allow to describe in more detail the reduction of risk bounds obtainable by this method in dependence on the degree of positive resp. negative dependence induced by the systematic risk factors. The insight may help in applications of this reduction method to get a better qualitative impression on the range of influence of the partially specified factor structure.