A time‐accurate pseudo‐compressibility approach based on an unstructured hybrid finite volume technique applied to unsteady turbulent premixed flame propagation

A preconditioning approach based on the artificial compressibility formulation is extended to solve the governing equations for unsteady turbulent reactive flows with heat release, at low Mach numbers, on an unstructured hybrid grid context. Premixed reactants are considered and a flamelet approach for combustion modelling is adopted using a continuous quenched mean reaction rate. An overlapped cell‐vertex finite volume method is adopted as a discretisation scheme. Artificial dissipation terms for hybrid grids are explicitly added to ensure a stable, discretised set of equations. A second‐order, explicit, hybrid Runge–Kutta scheme is applied for the time marching in pseudo‐time. A time derivative of the dependent variable is added to recover the time accuracy of the preconditioned set of equations. This derivative is discretised by an implicit, second‐order scheme. The resulting scheme is applied to the calculation of an infinite planar (one‐dimensional) turbulent premixed flame propagating freely in reactants whose turbulence is supposed to be frozen, homogeneous and isotropic. The accuracy of the results obtained with the proposed method proves to be excellent when compared to the data available in the literature. Copyright © 2004 John Wiley & Sons, Ltd.     

LES of turbulent heat transfer: proper convection numerical schemes for temperature transport

Large eddy simulations of two basic configurations (decay of isotropic turbulence, and the academic plane channel flow) with heat transfer have been performed comparing several convection numerical schemes, in order to discuss their ability to evaluate temperature fluctuations properly. Results are compared with the available incompressible heat transfer direct numerical simulation data. It is shown that the use of regularizing schemes (such as high order upwind type schemes) for the temperature transport equation in combination with centered schemes for momentum transport equation gives better results than the use of centred schemes for both equations. Copyright © 2004 John Wiley & Sons, Ltd.     

Assessment of two‐equation turbulence modelling for high Reynolds number hydrofoil flows

This paper presents an evaluation of the capability of turbulence models available in the commercial CFD code FLUENT 6.0 for their application to hydrofoil turbulent boundary layer separation flow at high Reynolds numbers. Four widely applied two‐equation RANS turbulence models were assessed through comparison with experimental data at Reynolds numbers of 8.284×106 and 1.657×107. They were the standard k–εmodel, the realizable k–εmodel, the standard k–ωmodel and the shear‐stress‐transport (SST) k–ωmodel. It has found that the realizable k–εturbulence model used with enhanced wall functions and near‐wall modelling techniques, consistently provides superior performance in predicting the flow characteristics around the hydrofoil. Copyright © 2004 John Wiley & Sons, Ltd.     

Particle correlations in e + e − → W + W − events

Preliminary results are reported on the two-particle correlation function R(Q) in hadronic Z decays, fully hadronic WW decays, and mixed hadronic-leptonic WW decays using data collected by the DELPHI detector at LEP at energies between 189 and 206 GeV. Evidence for Bose-Einstein correlations was observed in all three cases. The event mixing technique was used to determine correlations between particles arisingfrom different W bosons in fully hadronic WW decays. An excess of like-sign particle pairs with low four-momentum difference in fully hadronic WW events is observed, consistent with the effect expected from correlations between identical particles from different W bosons.     

Photoinitiators with functional groups. VII. Covalently bonded camphorquinone—amines

Camphorquinone (CQ), a widely used photoinitiator (PI) in dental applications, was covalently bonded to aromatic amines to enhance the rate of electron and proton transfer effect due to the close vicinity of the diketone and the amine group. 10‐bromocamphorquinone and 10‐bromomethylcamphorquinone were selected as suitable precursors for esterification with the carboxyl group containing aromatic amines based on 4‐dimethylaminobenzoic acid. Properties of the new photoinitiating systems were investigated by UV spectroscopy and differential scanning photocalorimetry in lauryl acrylate. Compared to physical mixtures, in all cases similar or even better performance was obtained. Surprisingly, 10‐acetyl derivatives 7 – 9 and 18 especially, were found to be highly reactive. Compared to CQ/ethyl 4‐dimethylaminobenzoate, the rate of photopolymerization was increased by a factor of up to 2. Intramolecular reaction was confirmed by photo‐differential scanning calorimetry experiments with varying PI concentrations. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4948–4963, 2004     

Tetrafunctional initiators for cationic polymerization of olefins

3,3′,5,5′‐Tetrakis(2‐chloro‐2‐propyl)biphenyl (biphenyl tetracumyl chloride, BPTCC) and 1,3‐bis[3,5‐bis(2‐chloro‐2‐propyl)phenoxy]propane (diphenoxypropane tetracumyl chloride, DPPTCC) were synthesized as initiators for quasiliving cationic polymerization of isobutylene (IB). In the synthesis of BPTCC, tetrafunctionality was achieved via the coupling of dimethyl 5‐bromoisophthalate (DMBI) using nickel dibromide bis(triphenylphosphine) and zinc in the presence of a base; in the synthesis of DPPTCC, two equivalents of dimethyl 5‐hydroxyisophthalate were linked via reaction with 1,3‐dibromopropane in the presence of potassium carbonate. Both initiators were used to initiate the polymerization of IB under quasiliving cationic polymerization conditions. PIB initiated from BPTCC revealed a chain end/molecule value (as determined by ¹H‐NMR) of 3.85, verifying the nearly exclusive production of 4‐arm polyisobutylene (PIB). GPC analysis revealed a narrow peak representing the target four‐arm PIB, with a slight shoulder at high elution volumes (low molecular weights). GPC analysis of the PIB initiated by DPPTCC revealed multimodal distributions, suggesting the formation of two‐, three‐, and four‐arm star polymers during the polymerization. This behavior was attributed to Friedel–Crafts alkylation of the initiator core after the addition of one IB unit, which was activated by the electron‐donating oxytrimethyleneoxy linking moiety. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5942–5953, 2004     

Viscoelastic behavior of polypropylene/nitrile rubber thermoplastic elastomer blends: Application of Kerner's models for reactively compatibilized and dynamically vulcanized systems

The viscoelastic properties of binary blends of nitrile rubber (NBR) and isotactic polypropylene (PP) of different compositions have been calculated with mean‐field theories developed by Kerner. The phase morphology and geometry have been assumed, and experimental data for the component polymers over a wide temperature range have been used. Hashin's elastic–viscoelastic analogy principle is used in applying Kerner's theory of elastic systems for viscoelastic materials, namely, polymer blends. The two theoretical models used are the discrete particle model (which assumes one component as dispersed inclusions in the matrix of the other) and the polyaggregate model (in which no matrix phase but a cocontinuous structure of the two is postulated). A solution method for the coupled equations of the polyaggregate model, considering Poisson's ratio as a complex parameter, is deduced. The viscoelastic properties are determined in terms of the small‐strain dynamic storage modulus and loss tangent with a Rheovibron DDV viscoelastometer for the blends and the component polymers. Theoretical calculations are compared with the experimental small‐strain dynamic mechanical properties of the blends and their morphological characterizations. Predictions are also compared with the experimental mechanical properties of compatibilized and dynamically cured 70/30 PP/NBR blends. The results computed with the discrete particle model with PP as the matrix compare well with the experimental results for 30/70, 70/30, and 50/50 PP/NBR blends. For 70/30 and 50/50 blends, these predictions are supported by scanning electron microscopy (SEM) investigations. However, for 30/70 blends, the predictions are not in agreement with SEM results, which reveal a cocontinuous blend of the two. Predictions of the discrete particle model are poor with NBR as the matrix for all three volume fractions. A closer agreement of the predicted results for a 70/30 PP/NBR blend and the properties of a 1% maleic anhydride modified PP or 3% phenolic‐modified PP compatibilized 70/30 PP/NBR blend in the lower temperature zone has been observed. This may be explained by improved interfacial adhesion and stable phase morphology. A mixed‐cure dynamically vulcanized system gave a better agreement with the predictions with PP as the matrix than the peroxide, sulfur, and unvulcanized systems. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1417–1432, 2004     

Thermal behavior of metallodendrimers possessing bis(terpyridinyl)Ru(II) connectivity and different surface functionality

A series of metallodendrimers, assembled by means of bis(terpyridinyl)Ru^(II) connectivity on poly(propylene imine) dendrimer scaffolds, with homogeneous or heterogeneous surfaces, were prepared. Differential scanning calorimetry and thermogravimetric analysis were used to determine their thermal behavior, glass‐transition temperatures, and the decomposition kinetics and temperatures; no synergy effects for these properties were observed for the heterogeneously surfaced constructs in contrast to the corresponding homogeneously coated materials, which exhibited different values depending on their surface functionalities. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1487–1495, 2004     

Dynamic surface tension measurements of surfactant solutions using the maximum bubble pressure method – limits of applicability

One of the essential differences in the design of bubble pressure tensiometers consists in the geometry of the measuring capillaries. To reach extremely short adsorption times of milliseconds and below, the so-called deadtime of the capillaries must be of the order of some 10 ms. In particular, for concentrated surfactant solutions, such as micellar solutions, short deadtimes are needed to minimize the initial surfactant load of the generated bubbles. A theoretical model is derived and confirmed by experiments performed for a wide range of experimental conditions, mainly in respect to variations in deadtime and bubble volume.     

Wide‐angle X‐ray diffraction and differential scanning calorimetry study of the crystallization of poly(ethylene naphthalate), poly(butylene naphthalate), and their copolymers

The crystallization behavior of a series of poly(ethylene‐co‐butylene naphthalate) (PEBN) random copolymers was studied. Wide‐angle X‐ray diffraction (WAXD) patterns showed that the crystallization of these copolymers could occur over the entire range of compositions. This resulted in the formation of poly(ethylene naphthalate) or poly(butylene naphthalate) crystals, depending on the composition of the copolymers. Sharp diffraction peaks were observed, except for 50/50 PEBN. Eutectic behavior was also observed. This showed isodimorphic cocrystallization of the PEBN copolymers. The variation of the enthalpy of fusion of the copolymers with the composition was estimated. The isothermal and nonisothermal crystallization kinetics were studied. The crystallization rates were found to decrease as the comonomer unit content increased. The tensile properties were also measured and were found to decrease as the butylene naphthalate content of the copolymers increased. For initially amorphous specimens, orientation was proved by WAXD patterns after drawing, but no crystalline reflections were observed. However, the fast crystallization of drawn specimens occurred when they were heated above the glass‐transition temperature. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 843–860, 2004