Diffusion-induced growth of compositional heterogeneity in polymer blends containing random copolymers

The compositional relaxation in random copolymer systems on a macroscopic scale is considered in theory. A set of diffusion equations is derived that describes the motion of chains of different composition and then converted into coupled equations for statistical moments of the compositional distribution. Several ways to solve the closure problem for these equations are discussed. The simplest is the situation when the shape of the transient compositional distribution can be predicted a priori, for example, a bimodal distribution is kept during interdiffusion of two copolymers that are not very close in composition. For a general case, it is shown that the cumulant-neglect closure based on the truncation of high-order cumulants is an effective method to get an approximate solution in terms of the time-dependent local mean composition and its dispersion. This method is applied to non-homogeneous compatible polymer systems, such as a random copolymer AB of a composition varying in space, a bilayer of Bernoullian copolymers AB of different composition, and a bilayer of homopolymers A and B, in which an autocatalytic polymer-analogous reaction A → B takes place, with possibility of the neighbor group effect. It is found that the interdiffusion can lead to a substantial broadening of the local compositional distribution, which, in turn, accelerates the system dynamics and promotes chemical reactions.     

Depletion effect on partial organization of atactic polymer chain segments in microcells

Glass transition for atactic poly(methyl methacrylate) (a-PMMA) prepared in nano-cells by microemulsion polymerization was measured at a faster heating rate after slow cooling of the sample from a temperature above T_g. An additional enthalpy relaxation and glass transition were observed at higher temperatures for the a-PMMA sample due to the partial organization of the chain segments which occurred during microemulsion polymerization. The re-precipitated a-PMMA did not show any self-organization under the same thermal conditions, although there are no changes in molecular weight or tacticity of the polymer chains. A depletion-interaction phenomenon was understood to provide entropic force for the self-organization of polymer chains inside the walls of the microemulsion cells.     

Reacting polymers with highly correlated initial conditions

We propose and theoretically study an experiment designed to measure short-time polymer reaction kinetics in melts or dilute solutions. The photolysis of groups centrally located along chain backbones, one group per chain, creates pairs of spatially highly correlated macroradicals. We calculate time-dependent rate coefficients κ(t) governing their first-order recombination kinetics, which are novel on account of the far-from-equilibrium initial conditions. In dilute solutions (good solvents) reaction kinetics are intrinsically weak, despite the highly reactive radical groups involved. This leads to a generalised mean-field kinetics in which the rate of radical density decay - ∼S(t), where S(t) ∼t ^{- (1 + g/3)} is the equilibrium return probability for 2 reactive groups, given initial contact. Here g≈ 0.27 is the correlation hole exponent for self-avoiding chain ends. For times beyond the longest coil relaxation time τ, - ∼S(t) remains true, but center of gravity coil diffusion takes over with rms displacement of reactive groups x(t) ∼t ^1/2 and S(t) ∼ 1/x ³(t). At the shortest times ( t 10^-6s), recombination is inhibited due to spin selection rules and we find ∼tS(t). In melts, kinetics are intrinsically diffusion-controlled, leading to entirely different rate laws. During the regime limited by spin selection rules, the density of radicals decays linearly, n(0) - n(t) ∼t. At longer times the standard result - ∼d ³(t)/d (for randomly distributed ends) is replaced by ∼d2x ³(t)/d ² for these correlated initial conditions. The long-time behavior, t > τ, has the same scaling form in time as for dilute solutions. Received 18 May 2000     

Characteristic variations in the effect of diluents on polymer crystallization and melting observed for a sample of poly(ethylene-co-octene)

Melting points in mixtures of a crystallizable polymer with a low-molar-mass diluent depend on both, the diluent fraction and the crystal thickness. A differentiation of the two factors can be achieved by temperature-dependent SAXS experiments. A corresponding study, complemented by DSC, dilatometry, microscopy and AFM-imaging, was carried out for mixtures of a poly(ethylene-co-octene) with n-C₁₆H₃₄, c-C₁₆H₃₂ and methyl-anthracene, respectively. All diluents lead for a constant crystal thickness to melting point depressions in agreement with Raoult's law. On the other hand, the effect of the diluents on the thickness of the crystals formed at a fixed crystallization temperature varies. While in the presence of the two alkanes thicker crystals form, no effect arises for the methyl-anthracene—as was previously found for the octene-co-units. We consider these observations as a further support for our view that polymer crystallization follows a multi-stage route which includes a passage through an intermediate mesomorphic phase. Under such conditions crystal thicknesses would only be affected if the diluent is still present in the mesomorphic phase and stay invariant if the diluent molecules are already rejected when this intermediate phase forms.     

Effect of ion irradiation on C 60 thin films

We report a new effect of ion irradiation on C₆₀ thin films: C₆₀ thin films irradiated with 7-MeV C²⁺ ions show resistance to photopolymerization. The resistance increases with increasing ion fluence of irradiation. The effect is qualitatively explained by the fact that the number of a C₆₀ pair satisfying the topochemical requirement for photochemical reaction in solids decreases by destruction of C₆₀ molecules accompanied by lattice disorder.     

Effects of NH3, O2, and N2 co-implantation on Cu out-diffusion and antimicrobial properties of copper plasma-implanted polyethylene

Metal antibacterial reagents are effective in the enhancement of the antimicrobial properties of medical polymers. However, incorporation of metal antibacterial reagents into polymers using conventional methods usually results in unstable antimicrobial effects. Our previous research demonstrates that plasma immersion ion implantation (PIII) can be used to effectively incorporate metal antibacterial reagents such as Cu into polyethylene (PE) in the near surface region up to several hundred nanometers without causing noticeable damage to the polymer matrix. In this work, various gases including NH₃, O₂, and N₂ were plasma-implanted in concert with Cu plasma immersion ion implantation to study the effects of these gas species on the release rate of Cu from the substrate. Our experimental results reveal that the copper depth profiles are not affected significantly by NH₃, O₂, or N₂ co-implantation and these gas elements have similar depth profiles as Cu. Chemical analyses demonstrate that polar functional CO, CO, CN, CN, and CN bonds formed in the substrate play an important role in regulating Cu out-diffusion. Among the three gas species, N₂ shows the best effects in regulating Cu out-diffusion and produces the best long term antibacterial properties. The Cu retention and out-diffusion mechanism in the ion-implanted polyethylene is described.     

Amphiphilic telechelic poly(N-isopropylacrylamide) in water: From micelles to gels<Superscript>⋆</Superscript>

We report the first study of aqueous solutions (0.025 gL^-1 to 46 gL^-1) of a telechelic poly(N-isopropylacrylamide) with octadecyl termini (C₁₈-PNIPAM-C₁₈, M_w: 37000, 320 NIPAM units, M_w/ M_n = 1.07) obtained by reversible addition-fragmentation chain transfer (RAFT) free radical polymerization of N-isopropylacrylamide. Static and dynamic light scattering measurements and fluorescence spectroscopy, using 8-anilino-1-naphthalenesulfonic acid (ANS) as probe, yielded the concentration dependence of the size and aggregation number of C₁₈-PNIPAM-C₁₈ micelles in cold ( 20^°C) dilute aqueous solutions. Concentrated solutions ( c > 20gL^-1) form transient gels exhibiting an oscillatory shear behavior that can be approximated by a single-relaxation Maxwellian model. Aqueous solutions of C₁₈-PNIPAM-C₁₈ undergo a phase transition upon heating to 31.5^°C as determined by microcalorimetry. The heat-induced phase separation of dilute (0.025 gL^-1) C₁₈-PNIPAM-C₁₈ solutions yields a fluid that is colloidally stable at temperatures higher than 33^°C. The overall results are consistent with a model assuming the formation of flowerlike micelles in the dilute regime and a network of micelles connected by telechelic chains in the concentrated regime.     

Laser-induced pattern formation in liquid sulfur

Liquid sulfur is a well-known liquid which exhibits a polymerization transition at T_p=159 °C. Recently, it was found from our experiments that such a transition can be induced below T_p through laser illumination and that an iridescent pattern appears under strong illumination with a pulsed laser of more than 60 mJ/cm² pulse. It is proposed that the visible change in iridescence is due to a macroscopic reconstruction of laser-generated polymers and that a laser-induced phase transition takes place from a freely expanded polymer phase to an ordered polymer phase when increasing the laser illumination. To further examine this possibility, the time variation of the iridescent pattern has been fully investigated using a macro lens, a polarized microscope and an optical microscope. In an analysis of the iridescent pattern, a rapid decrease in the area was observed after an initial slow decrease, suggesting a type of phase transition. Results from the observation of a quenched sulfur sample with a polarized microscope gave evidence that the iridescent region consists of polymers. Through observation of the liquid with a microscope, a striped pattern with micrometer sized spacing was noted in the iridescent pattern. A drastic color change was observed in the pattern from its generation to its disappearance. Sample thickness dependence of the pattern was also observed. These results were well explained by assuming the self-arrangement of laser-generated colloidal polymers.     

Plasma polymerization of styrene with carbon dioxide under glow discharge conditions

Plasma polymerization gains increasing interest for the deposition of films with functional properties suitable for a wide range of modern applications on account of its advantageous features. In this study, carbon dioxide (CO₂) was chosen as carrier gas at flow rates of 30 and 60 sccm, respectively and styrene vapor was used as the monomer to prepare polystyrene films on glass substrates. The structure and composition of the plasma polymerized films were characterized by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR) and compared with the film prepared by conventional thermal polymerization. The morphology information of the films was provided by optical microscopy. XPS and FT-IR results reveal that chemical composition of the plasma polymerized films is different from that of the thermal polymerized film and that oxygen content in the plasma polymerized films increases with the flow rate of CO₂. Furthermore, the presence of oxygen-containing groups on the surface of plasma polymerized polystyrene films is confirmed. It is also found that the composition and morphology of the plasma polymerized films are controlled by the flow rate of CO₂.     

The scaling behavior of the molecular parameters of the hyperbranched polymers made by self-condensing vinyl polymerization

The hyperbranched polymers can be made by self-condensing vinyl polymerization without gelation transition. The average molecular weights, as well as the average sizes, can reach infinite values as the reaction is quantitatively completed, and the scaling forms of the molecular parameters should exist. In the paper, based on a recursion formula, the scaling form of the number fraction distribution and the number of the n-mers are given analytically as the conversion of double bonds is near 1. The mean square radius of gyration for very large hyperbranched polymers is calculated explicitly to give a scaling exponent. Finally, a scaling relation associated with the fractal dimension and the polydispersity exponent is given clearly.     

Complex nanostructured materials from segmented copolymers prepared by ATRP

The development of new controlled/living radical polymerization processes, such as Atom Transfer Radical Polymerization (ATRP) and other techniques such as nitroxide mediated polymerization and degenerative transfer processes, including RAFT, opened the way to the use of radical polymerization for the synthesis of well-defined, complex functional nanostructures. The development of such nanostructures is primarily dependent on self-assembly of well-defined segmented copolymers. This article describes the fundamentals of ATRP, relevant to the synthesis of such systems. The self-assembly of block copolymers prepared by ATRP is illustrated by three examples. In the first, block copolymers of poly(butyl acrylate) with polyacrylonitrile phase separate, leading to spherical, cylindrical or lamellar morphologies, depending on the block copolymer composition. At a higher temperature, polyacrylonitrile block converts to nanostructured carbon clusters, whereas poly(butyl acrylate) block serves as a sacrificial block, aiding the development of designed nanostructures. In the second example, conductive nanoribbons of poly(n-hexylthiophene) surrounded by a matrix of organic polymers are formed from block copolymers prepared by ATRP. The third example describes an inorganic-organic hybrid system consisting of hard nanocolloidal silica particles (20 nm) grafted by ATRP with well-defined polystyrene-poly(benzyl acrylate) block copolymer chains (1000 chains per particle). Silica cores in this system are surrounded by a rigid polystyrene inner shell and softer polyacrylate outer shell. Received 9 July 2002 Published online: 11 March 2003     

Renormalization group analysis of boundary conditions in potential scattering

We analyze how a short distance boundary condition for the Schrödinger equation must change as a function of the boundary radius by imposing the physical requirement of phase shift independence on the boundary condition. The resulting equation can be interpreted as a variable phase equation of a complementary boundary value problem. We discuss the corresponding infrared fixed points and the perturbative expansion around them generating a short distance modified effective range theory. We also discuss ultraviolet fixed points, limit cycles, and attractors with a given fractality which take place for singular attractive potentials at the origin. The scaling behavior of scattering observables can analytically be determined and is studied with some emphasis on the low energy nucleon-nucleon interaction via singular pion exchange potentials. The generalization to coupled channels is also studied.     

High-throughput experimentation in synthetic polymer chemistry: From RAFT and anionic polymerizations to process development

The application of combinatorial and high-throughput approaches in polymer research is described. An overview of the utilized synthesis robots is given, including different parallel synthesizers and a process development robot. In addition, the application of the parallel synthesis robots to reversible addition fragmentation termination (RAFT) radical polymerizations and ionic copolymerizations is overviewed. Moreover, first results concerning the process development of semi-batch free radical polymerizations are described.     

Analysis of polymer adsorption onto colloidal particles

The structure of the layer formed after polymer adsorption onto a spherical particle is numerically studied by means of the application of the Single-Chain Mean-Field theory. We have determined several overall layer properties including the monomer volume fraction profiles, the layer thickness, adsorbances related to loops and to tails, as well as the variation of the crossover distance between loops and tails for different particle radii and fixed polymer length. When the radius of the sphere is small enough to affect the loop layer, one enters a single-adsorbed-chain regime, characterized by a critical sphere radius. In this regime, structural changes in the adsorbed layer arise. For such small sphere, the loop layer is confined to a region whose thickness is of the order of the radius of the adsorbing sphere, and two long tails dominate the outer layer and the adsorbance due to tails dominates that due to loops. An analysis of the structure of the outer tail layer for this small sphere case is also presented.     

Non-linear scission/recombination kinetics of living polymerization

Living polymers are formed by reversible association of primary units (unimers). Generally the chain statistical weight involves a factor σ < 1 suppressing short chains in comparison with free unimers. Living polymerization is a sharp thermodynamic transition for σ ≪ 1 which is typically the case. We show that this sharpness has an important effect on the kinetics of living polymerization (one-dimensional association). The kinetic model involves i) the unimer activation step (a transition to an assembly-competent state); ii) the scission/recombination processes providing growth of polymer chains and relaxation of their length distribution. Analyzing the polymerization with no chains but unimers at t = 0 , with initial concentration of unimers M ≳ M ^* (M^* is the critical polymerization concentration), we determine the time evolution of the chain length distribution and find that: 1) for M ^* ≪ M ≪ M ^*/σ the kinetics is characterized by 5 distinct time stages demarcated by 4 characteristic times t₁, t₂, t₃ and t^*; 2) there are transient regimes (t ₁ ≲ t ≲ t ₃) when the molecular-weight distribution is strongly non-exponential; 3) the chain scissions are negligible at times shorter than t₂. The chain growth is auto-accelerated for t ₁ ≲ t ≲ t ₂ : the cut-off chain length (= polymerization degree 〈n〉_w N ₁ ∝ t ² in this regime. 4) For t ₂ < t < t ₃ the length distribution is characterized by essentially 2 non-linear modes; the shorter cut-off length N₁ is decreasing with time in this regime, while the length scale N₂ of the second mode is increasing. (5) The terminal relaxation time of the polymer length distribution, t^*, shows a sharp maximum in the vicinity of M^*; the effective exponent is as high as ∼ σ^-1/3 just above M^*.     

Controlled structure and density of “living” polystyrene brushes on flat silica surfaces

Thin layers of polystyrene were grown from surface-grafted nitroxide initiators via controlled “living” free radical polymerization. The “reactive” Langmuir-Blodgett deposition method allowed an effective control of the initiator layer density leading to PS brushes with different and high grafting density and stretching. The influence of the grafting density on the layer structure was studied. Comparison with theoretical predictions for monodispersed brushes in bad solvent was discussed. The thickness was found to vary linearly with molecular weight and the density dependence was shown using wetting measurements. Special features of controlled radical nitroxide polymerization from a surface were discussed. A direct comparison of the molecular weight and polydispersity between surface and bulk polymers was made by de-grafting the brushes into a toluene/HF solution. Finally, some evidence of a “surface Fischer” effect was shown from re-initiated layers. Received 20 December 2001     

A FT-IR absorption analysis of vibrational properties of water encaged in NaA zeolites: evidence of a “structure maker” role of zeolitic surface

Linear polyisoprenes having dimethylamine end groups were prepared by high vacuum anionic polymerization techniques using 3-dimethylaminopropyllithium as the initiator. The amine group was reacted with 2-cholesteryl-2-oxo-1,3,2-dioxaphospholane to provide polymer chains having end zwitterionic groups chemically connected with cholesterol. The association behavior of these end-functionalized polymers was studied in cyclohexane by low angle laser light scattering, dynamic light scattering, and viscometry. The aggregation numbers, N _w were found to decrease by increasing the molecular weight of the precursor polymer, due to excluded volume repulsions. The ability of cholesterol to form liquid crystal mesophases facilitated the association process leading to higher N _w values. The hydrodynamic behavior of the aggregates was similar to that of star polymers. The dependence of the N _w values on the molecular weight of the base polymer, the polydispersity of the associates and the absence of critical micelle concentration, cmc are compatible with the linear head-packing model. Received 29 April 2002 and Received in final form 13 November 2002 Published online: 11 March 2003     

Measurement of adhesion energies and Young's modulus in thin polymer films using a novel axi-symmetric peel test geometry

We present a novel method of probing adhesion energies of solids, particularly polymers. This method uses the axi-symmetric deformation of a thin spincast polymer membrane brought into contact with a flat substrate to probe the work of adhesion. The use of a thin membrane minimizes uncertainty in the radius of contact, while the use of spincast films provides very smooth surfaces by means of a very simple method. The experimental profile of the deformed membrane shows good agreement with the expected logarithmic profile. The experimental setup enables the measurement of Young's modulus and the solid-solid work of adhesion for thin films. The value obtained for Young's modulus of polystyrene (PS) was found to be in agreement with other conventional measurement techniques. In addition, measurement of the work of adhesion at the PS/silicon oxide interface was possible. The apparatus is well suited to studying the dependence of Young's modulus, work of adhesion and fracture energy on membrane thickness, temperature, pulling rate, and ageing of the interface, and can readily be modified to study biologically relevant samples.     

Renormalization group analysis of a confined, interacting Bose gas

The renormalization group is not only a powerful method for describing universal properties of phase transitions, but it is also useful for evaluating non-universal thermodynamic properties beyond mean-field theory. In this contribution we concentrate on these latter aspects of the renormalization group approach. We introduce its main underlying ideas in the familiar context of the ideal Bose gas and then apply them to the case of an interacting, confined Bose gas within the framework of the random phase approximation. We model confinement by periodic boundary conditions and demonstrate how confinement modifies the flow equations of the renormalization group, thus changing the thermodynamic properties of the gas. Received: 20 July 2001 / Revised version: 20 August 2001 / Published online: 23 November 2001     

Molecular Dynamics simulation of a polymer chain translocating through a nanoscopic pore

The detection of linear polymers translocating through a nanoscopic pore is a promising idea for the development of new DNA analysis techniques. However, the physics of constrained macromolecules and the fluid that surrounds them at the nanoscopic scale is still not well understood. In fact, many theoretical models of polymer translocation neglect both excluded-volume and hydrodynamic effects. We use Molecular Dynamics simulations with explicit solvent to study the impact of hydrodynamic interactions on the translocation time of a polymer. The translocation time τ that we examine is the unbiased (no charge on the chain and no driving force) escape time of a polymer that is initially placed halfway through a pore perforated in a monolayer wall. In particular, we look at the effect of increasing the pore radius when only a small number of fluid particles can be located in the pore as the polymer undergoes translocation, and we compare our results to the theoretical predictions of Chuang et al. (Phys. Rev. E 65, 011802 (2001)). We observe that the scaling of the translocation time varies from τ ∼ N ^11/5 to τ ∼ N ^9/5 as the pore size increases (N is the number of monomers that goes up to 31 monomers). However, the scaling of the polymer relaxation time remains consistent with the 9/5 power law for all pore radii.