Linear polymers in nonhomogeneous flow fields. I. Translational diffusion coefficient

The translational diffusion coefficient D, needed in treatments of flow-induced polymer migration phenomena, is studied. Explicit results are reported for bead–spring model macromolecules with two, three, and four beads, respectively. If the number of beads is large, an integral formulation is used. The results obtained show that D depends upon the hydrodynamic interaction parameters h^* and h^*N^1/2. Nondraining behavior of D is predicted irrespective of h if h^* is close to 0.2357. Approximations for D are obtained and the error involved is estimated.     

The origin of polymer migration in a nonhomogeneous flow field

Flow-induced polymer migration is treated in a rather intuitive though mathematically formal way. It is important to incorporate hydrodynamic interaction effects as well as flow geometry effects in studying polymer migration perpendicular to the flow direction. Simple examples, circular Couette flow in the free-draining limit and plane Poiseuille flow in the nondraining limit, are chosen to illustrate the importance of such effects.     

Thermally reversible polymer linkages. II. Linear addition polymers

The stepwise addition polymerization reactions of bisazlactones [bis(2-oxazolin-5-one)s] and a variety of 4,4′-bisphenols have been studied for the purpose of making thermally reversible linear polymers. Thus polymerization occurs at or near room temperature, while depolymerization yielding the two monomer species occurs at elevated temperatures. The synthesis of oligomers in solution without the use of catalyst occurs for the reaction of bisazlactones with bisphenols containing an electron-withdrawing moiety between the two phenol groups of the bisphenol. These oligomers regenerate the bisphenol and bisazlactone monomers upon heating to 165–200°C for several hours under dry box conditions. In many cases, these reactions follow the same patterns of reactivity observed in model studies. This chemistry may be useful for forming degradable or recyclable polymers, where shortchain prepolymers, or macromonomers, endcapped with azlactone and phenol moieties could be used to form high molecular weight polymers that are thermoreversible. Such a reaction system might also be used for preventing reactions of bisphenols and/or bisazlactones at low temperatures, with the desired reaction initiated by formation of the reactive species at elevated temperatures. Envisioned uses in this case might be thermally triggered crosslinking or polymerization reactions, or temperature controlled drug release. © 1993 John Wiley & Sons, Inc.     

Diffusion in glassy polymers. II

The Fickian diffusion coefficient of methylene chloride in a glassy epoxy polymer is calculated with the use of Crank's model of discontinuous change of D with concentration C. The diffusion constant is obtained as 1.93 × 10^?6 cm²/sec. The swollen layer behind the advancing solvent front is essentially in the rubbery state of the same polymer. The case II swelling by benzene is discussed in terms of a convective transport arising from the partial stress (internal) tensor of the penetrant. The superposition of Fickian and case II diffusion found with mixtures of methylene chloride and benzene is also discussed briefly.     

Internal motion in organosilicon polymers. I. Linear dimethylpolysilazane

A linear dimethylpolysilazane polymer has been prepared and its internal motion studied by the techniques of broadline nuclear magnetic resonance. Second moments and line widths are reported as a function of temperature from ?196 to 30°C. The results are compared to those for linear dimethylpolysiloxane, as well as to those for the crosslinked siloxane and silazane. The experimental low-temperature second moment of 7.25 ± 0.5 gauss² corresponds to a C₃ reorientation of methyl groups about the silicon–carbon bond. The motions occurring in the silazane are found to be the same as those in the corresponding siloxane. The transition to low second moments occurs approximately 30°C. higher in the linear silazane than in the linear siloxane. This is attributed to a somewhat greater resistance to motion in the silazane.     

Cholesteric polymers in electric fields

Abstract

The main peculiarities of electric field-induced structural transformations in cholesterol containing comb-shaped polymers are discussed. As for low molar mass cholesterics both the changes in the texture and the untwisting of the helix can be observed. In cholesteric copolymers with a layered order of the side chains the untwisting of the helix results in the formation of a smectic-like structure. The dynamics of the helix untwisting is shown to be controlled by the mobility of the backbone.     

Cholesteric polymers in electric fields

The main peculiarities of electric field-induced structural transformations in cholesterol containing comb-shaped polymers are discussed. As for low molar mass cholesterics both the changes in the texture and the untwisting of the helix can be observed. In cholesteric copolymers with a layered order of the side chains the untwisting of the helix results in the formation of a smectic-like structure. The dynamics of the helix untwisting is shown to be controlled by the mobility of the backbone.     

Intercomparison of slip flow velocity measurements of filled polymers by capillary extrusion rheometry

Slip flow can complicate both the measurement of the shear flow behaviour of polymers and the modelling of moulding processes. However, the understanding of the reliability of methods for measuring slip flow behaviour is limited. The results of an intercomparison on the measurement of slip flow behaviour by capillary extrusion rheometry of two polymer melts—a filled high-density polyethylene and a filled ethylene–vinyl acetate copolymer—are reported. Slip velocities were calculated, following the Mooney method, from the dependence of the shear stress–shear rate behaviour on the extrusion die diameter. Both compounds exhibited wall slip: in one case the slip velocity accounted for ≈80% of the total flow rate. Slip velocity results were typically within ≈±20% of the average values for the materials, although scatter up to ≈±40% was obtained for one material at high shear stresses. An analysis of slip velocity measurements indicated that uncertainties of 40–50% are typical (95% confidence level) although significantly higher uncertainties could result if testing conditions (primarily die diameters) are not optimised.     

Chemorheology of linear polymers. II

The chemical stress relaxation of crosslinked polymers had long been studied. The chemorheology of linear polymers is difficult to study because molecular flow by diffusion is generally much more rapid than relaxation or flow caused by chemical reaction. Our previous paper dealt with the chemorheology of linear polymers on taking such physical flow into consideration. By using another modified expression suggested by Tobolsky, good consistency between the theoretical chemical stress relaxation curve and an experimental one was obtained for polydisperse polystyrene and the commercial polystyrene used.     

Persistent polarization in polymers. II. Depolarization currents

Depolarization currents were used to study the persistent polarization induced in polystyrene and poly(methyl methacrylate) by cooling with flow under pressure. These studies showed that the charge on electrets made by flow under pressure consists in part of a surface charge which leaks off rapidly in moist air and in part of a charge due to volume polarization which decays more slowly. The volume polymerization produced in poly(methyl methacrylate) by flow under pressure is of the same order as that produced by cooling under a voltage drop, but flow under pressure produces a larger surface charge.     

Intumescent flame retardants for polymers. II. The polypropylene-ammonium polyphosphate-polyurea system

The mechanism of action of ammonium polyphosphate (APP) and polyurea (PU) as flame retardant (FR) agents for polypropylene (PP) was examined. The APP–PU system behaves as an intumescent flame-retardant (IFR) formulation. Comparison of the oxygen index (OI) measured on molded pellets and rods, values of the polymer temperature measured just below the burning surface, and visual considerations describe the IFR action of this system. A strong synergism between APP and two of the four polyureas investigated here was ascertained with a maximum 3:1 ratio. Thermogravimetric (TG), OI, nitrous oxide index (NOI), and char-residue measurements were made. On the basis of our data, it can be concluded that polyurea acts as a catalyst for the charring reactions of the APP on PP.     

Metal coordination polymers. II. Molecular weight studies of beryllium phosphinate polymers in toluene

The number-average molecular weights of beryllium 4-biphenyl(phenyl)phosphinate, di-n-pentylphosphinate, di-n-heptylphosphinate, and trifluoromethyl(phenyl)phosphinate are degraded by the presence of water in toluene. It is proposed that easily hydrolyzable P? O? P bonds contribute, in part, to the bonding of these polymers.     

Polyethylene-polystyrene gradient polymers. II. The swelling-induced crystallization in the PE-PS gradient polymers and modified by styrene LDPE samples

In this paper, the swelling-induced crystallization effect observed in gradient polymers and in low density polyethylene modified by styrene is discussed. The polymerization-induced crystallization in the PE-PS gradient polymers is demonstrated and its influence on the crystalline phase stability in the LDPE matrix exhibited. Some new information about the specific, internal structure of the gradient polymers is presented, which confirms the differences between formation of these substances and other gradient polymers previously investigated.     

Dilute solution properties of a polyurethane. I. Linear polymers

A linear polyurethane of high molecular weight was prepared in solution by the polyaddition of equimolar amounts of ethylene glycol and methylene bis(4-phenyl isocyanate). The polymer was fractionated by using a direct sequential extraction procedure, with a solvent–nonsolvent system consisting of N,N′-dimethylformamide (DMF) and acetone (A). The resulting fractions were characterized by viscosity and lightscattering measurements. The relationship between the intrinsic viscosity and molecular weight was found in DMF at 25°C. to be [η] = 3.64 × 10^?4M^0.71. The unperturbed polymer chain dimensions were determined from intrinsic viscosity measurements carried out under experimentally determined theta conditions.     

Dehydrochlorination reactions in polymers. Part II. Chlorinated polystyrene

The dehydrochlorination of chlorinated polystyrene was studied in the temperature range 120–220°C., when HCl was the sole volatile product. The dehydrochlorination was accompanied by the slow development of color and chain scission. The elimination rate fell too rapidly with reaction extent to be accounted for by reduction of reagent. Solution studies in o-dichlorobenzene indicated that the reaction was initially first-order in polymer concentration but was retarded by the polyene reaction products. The overall elimination was interpreted as a radical process in which the product was an active retarder. These observations are also valid for the elimination of HBr from brominated polystyrene.     

A Brownian dynamics-finite element method for simulating DNA electrophoresis in nonhomogeneous electric fields

The objective of this work is to develop a numerical method to simulate DNA electrophoresis in complicated geometries. The proposed numerical scheme is composed of three parts: (1) a bead-spring Brownian dynamics (BD) simulation, (2) an iterative solver-enhanced finite element method (FEM) for the electric field, and (3) the connection algorithm between FEM and BD. A target-induced searching algorithm is developed to quickly address the electric field in the complex geometry which is discretized into unstructured finite element meshes. We also develop a method to use the hard-sphere interaction algorithm proposed by Heyes and Melrose [J. Non-Newtonian Fluid Mech. 46, 1 (1993)] in FEM. To verify the accuracy of our numerical schemes, our method is applied to the problem of lambda-DNA deformation around an isolated cylindrical obstacle for which the analytical solution of the electric field is available and experimental data exist. We compare our schemes with an analytical approach and there is a good agreement between the two. We expect that the present numerical method will be useful for the design of future microfluidic devices to stretch and/or separate DNA.     

Theoretical models for diffusion in glassy polymers. II

The author refines and generalizes a model for diffusion in glassy polymers which he previously introduced. The model unifies many diverse observations by explicity formulating the common property of a glassy polymer in all its various modes, namely the finite relaxation time due to its slow response to changing conditions. An integral approximation method is used to study the motion of the penetrant front and the glass-gel interface and a useful polynomial approximation method is introduced for use in special simple situations.