Effect of polydispersity on the viscosity of a suspension of hard spheres

A simple procedure is suggested for calculating the concentration dependence of the viscosity of a suspension of two types of hard spheres, which have considerably different diameters. It is shown that for the calculations it is sufficient to know the concentration dependence of the suspension viscosity of monodisperse hard spheres.     

Calculation and experimental verification of concentration profiles for selected species at the interphase generated by diffusion in polymer pairs

A method for calculating diffusion rates for individual species in concentrated regime is outlined. The effects of monomeric friction coefficient, Flory–Huggins thermodynamic interaction parameter, individual species molecular weights, local molecular weights distribution, and local T_g are precisely calculated. The method is used to calculate individual concentration profiles generated by diffusion of multicomponent polymer blends, and experimentally tested. Polystyrene with a bimodal molecular weight distribution is allowed to diffuse in a blend of polyphenylene oxide and polystyrene. Local physical properties change markedly along the interdiffusion path and, therefore, this is a demanding test for the proposed calculation method. The simulated concentration profiles are compared with results obtained by using two independent experimental techniques: Raman spectroscopy and dynamic mechanical analyzer (DMA). The total polystyrene (PS) concentration profiles, calculated using the proposed method, agree well with Raman spectroscopy results. Simulated DMA results—which are sensitive to the PS species molecular weight distribution—obtained using the concentration profiles, calculated for each PS molecular weight species agree well with the experimental DMA results. Calculations based on average molecular weights give incorrect results. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 3097–3107, 1999     

Reversible Addition-Fragmentation Chain Transfer Polymerization of Methyl Methacrylate in Microemulsion: The Influence of Reaction Conditions on Polymerization

The reversible addition-fragmentation chain transfer (RAFT) polymerization of methyl methacrylate (MMA) using cetyltrimethylammonium bromide (CTAB) as surfactant and a difunctional RAFT agent S,S′-bis (α, α′-dimethylacetic acid) trithiocarbonate (BDAT) as chain transfer were conducted in microemulsion. The influence of polymerization temperature and concentration of RAFT agent on the polymerization were investigated, respectively. The results showed that the molecular weight of products increased linearly with conversion, the polydispersity indexes remained low value, and the polymerization processes were totally under control with increasing concentration of RAFT agent, the polymerization behavior exhibited living polymerization characters. In addition, the influence of RAFT concentration on the particle size was investigated by TEM. The results indicated that the particles were highly monodispersed and the particle size increased with increasing concentration of RAFT agent.     

Novel acid initiators for the rapid cationic polymerization of styrene in room temperature ionic liquids

Cationic polymerization of styrene has been achieved using several novel acidic initiators in room temperature ionic liquids (ILs) under mild reaction conditions to obtain polymers of low molecular weight with narrow polydispersity. Both strong protic acids such as bis(trifluoromethanesulfonyl) amide acid (HTFSA) and a moderately weak acid such as bisoxalato phosphorous acid (HBOP) have been studied as initiators. It has been observed that HTFSA initiates the polymerization rapidly even at room temperature and below, as compared to HBOP which produces a slower polymerization requiring elevated temperatures to complete. The relative difference in reactivity of the initiators as compared to the previously described HBOB initiator is discussed in terms of the difference in their proton acidity and the consequential basicity of the anions. The efficiency of different ILs as the reaction solvent is also presented.     

Rheology of concentrated suspensions containing mixtures of spheres and fibres

Optimising flow properties of concentrated suspensions is an important issue common for many industries. The rheology of concentrated suspensions has therefore been studied intensively both experimentally and theoretically. Most studies have focused on monodisperse and polydisperse suspensions of either spheres or fibres. In practice, most suspensions contain particles that are polydisperse both in size and shape. A mixing rule for such systems is expected to be a powerful tool for engineers and product designers. Therefore in this work, suspensions of spheres, fibres and mixtures thereof were characterised using rotational shear rheometry and in-line image analyses. Thereby, total solids volume concentration and fibre fraction was varied. Results from transient and steady-state shear rheometry are discussed with respect to concentration, fibre fraction, and shear induced microstructure. Experimentally obtained viscosity data were accurately fitted using the model proposed by Farris (T Soc Rheol 12:281, 1968) for mixtures of monodisperse non-interacting spheres of different sizes.Originally presented at the Annual European Rheology Conference 2003, AERC 2003     

A novel amphipathic block copolymer coating forming micelle-like aggregates for separation of steroids in open tubular capillary electrochromatography

A new amphipathic block copolymer, poly(tert-butyl acrylate)₁₂₇-block-poly(glycidyl methacrylate)₈₆, was developed for the coating in open tubular capillary electrochromatography. The self-assembly characters of the coating, which could form micelle-like aggregates under proper conditions, were observed by atomic force microscopy. Compared with bare capillary, this coating could act as surfactant and lead to improve the separation of steroids. In addition, the influence of pH, buffer concentration and organic solvents on the separation was investigated. The best separation of the three model steroid analytes could be achieved using 20.0 mM borate buffer at pH 10.5. For covalent bonding, the coating showed good repeatability and stability with RSD of u_EOF less than 3.3%. Then, this proposed method was well validated with good linearity (≥0.999), recovery (91.0-94.0%) and repeatability, and was successfully used for separation of steroids in spiked serum samples, which indicated that this new OT-CEC method could provide a potential tool to determine steroids in real biological system without interference.     

Quasiliving Carbocationic Polymerization. XVI. Forced Ideal Terpolymerization of Styrene-α-Methylstyrene-lsobutylene

Forced ideal carbocationic terpolymerization of styrene/α-methylstyrene/isobutylene systems has been achieved by continuous addition of mixed monomer feeds to 2-chloro-2,4,4-trimethylpentane/TiCl₄ initiator/coinitiator charges dissolved in n-hexane/methylene chloride solvent mixtures. The compositions of terpolymers were uniform and identical to those of the feeds in the concentration ranges studied. The number-average molecular weights increased monotonously with the amounts of monomers consumed; however, pronounced chain transfer to monomer was evident. The microstructure of the products was investigated ¹³C-NMR spectroscopy. According to dual detector GPC, ¹³C-NMR and DSC data true terpolymers have formed.     

Synthesis of poly(4‐vinylpyridine) by reverse atom transfer radical polymerization

Controlled radical polymerization of 4‐vinylpyridine (4VP) was achieved in a 50 vol % 1‐methyl‐2‐pyrrolidone/water solvent mixture using a 2,2′‐azobis(2,4‐dimethylpentanitrile) initiator and a CuCl₂/2,2′‐bipyridine catalyst–ligand complex, for an initial monomer concentration of [M]₀ = 2.32–3.24 M and a temperature range of 70–80 °C. Radical polymerization control was achieved at catalyst to initiator molar ratios in the range of 1.3:1 to 1.6:1. First‐order kinetics of the rate of polymerization (with respect to the monomer), linear increase of the number–average degree of polymerization with monomer conversion, and a polydispersity index in the range of 1.29–1.35 were indicative of controlled radical polymerization. The highest number–average degree of polymerization of 247 (number–average molecular weight = 26,000 g/mol) was achieved at a temperature of 70 °C, [M]₀ = 3.24 M and a catalyst to initiator molar ratio of 1.6:1. Over the temperature range studied (70–80 °C), the initiator efficiency increased from 50 to 64% whereas the apparent polymerization rate constant increased by about 60%. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5748–5758, 2007     

Spherical and Cylindrical Low-Amplitude Waves in Polydisperse Fogs with Phase Transitions

A linear theory of propagation of spherical and cylindrical disturbances in polydisperse gas-vapor-drop mixtures is developed. Unsteady and non-equilibrium effects in the interphase mass, momentum, and energy exchange are taken into account. A general dispersion relation determining the propagation of plane, spherical, and cylindrical harmonic disturbances in polydisperse gas-vapor-drop systems is obtained. Using the fast Fourier transform, the propagation of pulse disturbances of different shapes in mixtures of air with water vapor and water drops is calculated. The effect of the geometry and interphase heat and mass transfer on the evolution of weak pulses in polydisperse air fogs is investigated.