Unusual thermal diffusion in polymer solutions

Thermal diffusion forced Rayleigh scattering results on thermal diffusion of poly(ethylene oxide) (PEO) in ethanol/water mixtures are presented. In water-rich solvent mixtures, PEO is found to migrate towards regions of lower temperature. This is typical for polymer solutions and corresponds to a positive Soret coefficient of PEO. In solvent mixtures with low water content, however, the polymer is found to migrate towards higher temperatures, corresponding to a negative Soret coefficient of PEO in ethanol-rich solutions. To our knowledge, this is the first observed sign change of the Soret coefficient of a polymer in solution. We also present a simple lattice model for the polymer solvent system and calculate Soret coefficients with statistical mechanics methods. The calculated values agree qualitatively with the experimental results.     

聚环氧乙烷在水和叔丁醇溶液中分子构型变化的研究

在聚合物溶液中,聚合物单体和溶剂分子之间的相互作用会影响聚合物高分子的尺寸和结构。本文使用动态光散射实验系统研究了聚环氧乙烷在水+TBA二元混合溶液中的分子尺寸变化,实验结果表明聚环氧乙烷分子会呈现出收缩-膨胀的奇异性构型变化。本文也系统分析了产生该现象的原因,依次分析了在二元混合溶液中可能对聚合物分子尺寸产生影响三个原因:溶剂非理想性影响(Shultz-Flory理论)、临界涨落影响以及水+醇溶液所呈现出来的奇异性性质。结合这三个因素,本文较好地解释了实验所观测到的奇异现象。     

Scientific Review: Interactions of PEO with Monovalent Electrolytes in Solvents of Different Hydrogen Bonding Capacities

Small-Angle Neutron Scattering (SANS) has been used in order to investigate the ion binding capacities of PEO in different solvents. Aprotic (acetonitrile) as well as protic (methanol and water) solvents, have been studied where methanol and water form an average two and four tetrahedrally oriented hydrogen bonds per molecule, respectively [1]. Unusual behavior of PEO has been observed in aprotic solvents and solvents with moderate hydrogen bonding where monovalent ions associate to the polymer backbone leading to a polyelectrolyte-like (where a certain fraction of monomers are charged) behavior. This is in marked contrast to behavior in aqueous solutions where water molecules associate via hydrogen bonding to the polymer and the ions are more preferentially coordinated by the solvent than the polymer.     

Monte Carlo simulations of an amphiphilic polymer at a hydrophobic/hydrophilic interface

Monte Carlo simulations have been carried out for an off-lattice model of an amphiphilic polymer at a hydrophobic/hydrophilic interface. The model system consists of a polynorbornene backbone with poly(ethylene oxide) (PEO) grafts modelled atomistically at an idealized interface between hydrophobic and hydrophilic regions, which are represented by external potentials. Results are presented for the distribution of PEO chain ends, and the density of PEO segments perpendicular to the surface. The latter is used to provide predictions for neutron reflectivity profiles normal to the surface as a function of the lateral confinement of the PEO grafts. At low surface coverage the simulation results are found to be in good agreement with experimental neutron scattering results from similar polymers studied at the water/air interface.     

Annealing polyelectrolytes at charged interfaces

The conformation of a weakly dissociating (annealing) polyelectrolyte chain end-tethered to a similarly or oppositely charged planar surface is analyzed in the framework of scaling arguments. For a similarly charged interface an analytical model is also utilized. We demonstrate that at low salt concentration in bulk solution there is a strong coupling between the polyelectrolyte conformation and its degree of ionization. In the case of an oppositely charged (adsorbing) surface, adsorption promotes ionization of the annealing polyelectrolyte. As a result, the adsorbed layer thickness decreases as a function of surface charge density more rapidly for an annealing polyelectrolyte than for a quenched one. In the case of a similarly charged (repulsive) surface the chain ionization is suppressed, and the annealing polyelectrolyte chain is less extended than the quenched one. Moreover, an increase in surface charge density leads to non-monotonous extension of the tethered polyelectrolyte.Received: 16 September 2003, Published online: 5 February 2004PACS: 61.25.Hq Macromolecular and polymer solutions; polymer melts; swelling - 82.35.Gh Polymers on surfaces; adhesion - 82.35.Rs Polyelectrolytes     

Effects of preparation method on properties of lithium salt-poly(ethylene oxide) polymer electrolytes

The effects of using different sources of precursor poly(ethylene oxide) (PEO) and acetonitrile solvent on the physical and electrochemical properties of lithium salt-PEO polymer electrolytes were investigated. Although no differences were found due to the use of different types of PEO, the purity of the acetonitrile solvent was found to be critical in controlling the properties of the polymer product. Acetonitrile of nominally relatively low purity produced polymer electrolytes exhibiting largely crystalline type behaviour while the use of nominally high purity solvents gave polymers which were apparently completely amorphous at temperatures above about 50°C. Transport number measurements gave values for the lithium ions of 0.4 at 132°C for the largely crystalline materials and 0.3 at 112°C for the amorphous polymers. Analysis of the acetonitrile solvents revealed the presence of water in the nominally high purity grades and it has been confirmed that water contamination is responsible for the production of the low melting temperature form of the polymer complex.     

On the conformation and the structure of polymacromonomers

Using poly( -norbornenyl polystyrene) as a model we studied the conformation and the structure of branched polymer chains each of whose backbone constitutive units bear a branch. The parameters taken into account are: the polymerisation degree of the backbone, the molar mass of the branches and the solution concentration. The effect of the global conformation of these polymacromonomers, either spherically or cylindrically (vermiform) symmetric, is considered. The compactness of the polymer constitutive unit distribution, the branches and the backbone conformations are considered as functions of the first two parameters above. Significant results are obtained on all of these three points.Received: 24 May 2004, Published online: 21 September 2004PACS: 61.12.Ex Neutron scattering - 61.41. + e Polymers, elastomers, and plastics - 61.46. + w Nanoscale materials: clusters, nanoparticles, nanotubes, and nanocrystals     

Shear-induced concentration fluctuations and form factor changes in polymer solution in the good-solvent regime

Small-Angle Scattering from sheared semidilute polymer solution is reported in the good-solvent regime, at variance with former light and neutron measurements in the regime. First, concentration fluctuations are observed: the scattering increases noticeably along the flow at low q, but at variance with former results for the theta-solvent regime, no demixing is observed at higher shear. Here, instead, the effects follow a time-temperature superposition and saturate above a Weissenberg number around 5, like the stress which is known to present a plateau for these systems. Using the Zero Average Contrast technique, we have also measured the form factor, which displays the same saturation effect reaching a deformation ratio of the order of 2. These results agree with the Convective Constraint Release models (CCR) elaborated in order to predict the stress effects in the non-Newtonian regime (Marrucci-Ianniruberto) and their extension predicting also the scattering (Likhtman-Milner-McLeish).Received: 5 July 2004, Published online: 1 October 2004PACS: 61.12.Ex Neutron scattering (including small-angle scattering) - 47.15.-x Laminar flow - 61.25.Hq Macromolecular and polymer solutions; polymer melts; swelling     

Solid-state NMR studies of the crystalline and amorphous domains within PEO and PEO: LiTf systems

Solid polymer electrolytes (SPEs) contain amorphous and crystalline regions, each of which have unique contributions to the ¹³C NMR spectrum. Understanding and assigning the ¹³C NMR signals are vital to interpreting the NMR data collected for each phase. The ¹³C CPMAS solid-state NMR spectrum of poly(ethylene oxide), a common polymer electrolyte host material, has superimposed broad and narrow components. Previously, the narrow component has been assigned to the amorphous region and the broad component to the crystalline PEO fraction. These assignments for pure PEO have been applied to various PEO:salt systems. Using lithium triflate salt dissolved in PEO, we revisit the spectral assignments and discover that the narrow component is due to crystalline PEO:LiTf component, which is reversed from the previous pure PEO assignment. This paradigm shift is based on data collected from a 100% crystalline PEO:LiTf with a 3:1 oxygen:lithium ratio sample, which exhibited only the narrow peak. For dilute electrolytes, such as 20:1 PEO:LiTf, the ¹³C CPMAS spectra contain the narrow peak superimposed on a broad peak as seen with pure PEO. As dilute electrolytes are heterogeneous with crystalline and amorphous regions of both pure PEO and PEO:LiTf complex, peak assignments for pure PEO and PEO:LiTf are important. Thus, we reexamine the previous assignment for pure PEO using samples of pure powdered PEO, thermally treated pure powdered PEO, and a thin film PEO cast from an acetonitrile solution. With these different samples, we observed the growth of the narrow peak under conditions that favor crystallization. Therefore, for pure PEO, we have reassigned the narrow peak to the crystalline region and the broad peak to the amorphous region. In light of our observations, previous NMR studies of pure PEO and PEO SPEs should be reinvestigated. We also use rotational echo double resonance (REDOR) to study the 20:1 PEO:LiTf created from 2 and 100 kDa PEO. We find that the lithium environment is similar in the respective microcrystalline domains. However, the 100 kDa samples have a larger fraction of pure crystalline PEO.     

表面张力对PEO稀溶液粘度行为的影响

测定了不同分子量聚氧化乙烯 (PEO)在水和苯溶剂中的粘度 ,发现在低浓度区PEO水溶液的比浓粘度出现负偏离 ,PEO苯溶液比浓粘度与浓度之间依旧满足线性关系 .表面张力测定结果表明 ,PEO分子显著降低了水的表面张力 ,而苯的表面张力则不受影响 .PEO水溶液和纯溶剂水表面张力的不同干扰了高分子溶液和溶剂在粘度计中流过时间的测量 ,导致低浓度区PEO水溶液比浓粘度出现负偏离 .利用PEO水溶液和水表面张力测定结果 ,结合乌式粘度计的几何尺寸 ,定量分析了PEO水溶液和纯溶剂水表面张力的差异对粘度测量结果的影响 ,计算结果与实验结果基本相符 .如果用PEO水溶液流过时间对浓度作图的外推值t0 计算相对粘度 ,可以完全消除PEO水溶液和水表面张力差异对粘度测量的影响     

Heats of solution and dilution for polyethylene oxide in several solvents

The Tian-Calvet microcalorimeter, as modified by Maron and Filisko, has been used to measure the heats of solution and dilution of a sample of polyethylene oxide (PEO) of M₂ = ca. 6000 in chloroform, methylene chloride, and water. By applying the Maron theory to these measurements, it was found from the organic solvent data that the heat of fusion of the PEO sample is 57.1 cal/g polymer, independent of the solution concentration or the solvent used. However, the solution behavior in water was different because PEO in organic solvents exists as a random coil, whereas in water its conformation is helical. By combining the water and organic solvent data, it can be shown that conversion of the random coils to the helix involves the evolution of 39.3 cal of heat per gram of polymer. This heat evolution accounts, in all probability, for the solubility of PEO in water.     

Neutron scattering and compressibility measurements for the study of hydration effects on polymeric aqueous solutions

Summary The present paper reports the results of compressibility and incoherent quasi-elastic neutron scattering measurements performed on polymeric systems and on their aqueous solutions. From the compressibility data, the temperature evolution of the polymer hydration number can be derived. On the other hand, neutron data show that the translational diffusion coefficientD _T turns out to be higher in the case of ethylene glycol + water, with respect to that of pure, suggesting that the water molecules act as a ?structure breaker? of the intermolecular connectivity existing into the pure. Furthermore the dynamical properties of the H₂O molecules in the presence of poly(ethylene glycol) deeply differ from those in the bulk, and show that we are in the presence of entangled water. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Extensive stretch of polysiloxane network chains with random- and super-coiled conformations

The stress-elongation relations at large deformations for the polymer network chains with randomcoiled and supercoiled conformations are investigated using the polysiloxane networks with high elongations at break far over 10. Supercoil is the conformation of network chains in deswollen polymer networks which are made by removing solvent from the networks crosslinked in solutions at low polymer concentrations. The validity of the scaling concept of Pincus blob for the mechanical response of a polymer chain is experimentally confirmed for the network composed of randomcoiled chains. The analysis of the stress- relations for the deswollen networks comprised of supercoiled chains on the basis of the Pincus blob concept suggests that supercoil is a much more contracted conformation relative to randomcoil. Received: 25 August 1997 / Received in final form: 13 October 1997 / Accepted: 22 January 1998     

Structure of hydrophobically and hydrogen-bonded complexes between amphiphilic copolymer and polyacid in water

We observed by SANS and NMR the structure of intermolecular complexes formed through hydrogen bonding and hydrophobic interactions between a polyacid and a neutral copolymer surfactant (PEO-PPO-PEO). The polyacid is perdeuterated and the contrast variation method enables us to measure separately the structure factor of each component in the complex and the cross structure factor as a function of the pH and the temperature. The evolution of NMR spectra and relaxation times with pH and temperature give a complementary insight into the inner structure of the aggregates. The interaction between the aggregates and the aggregation number of polyacid chains are governed by electrostatic effects; they depend on the polyacid charge and are insensitive to temperature. The number of copolymer chains which results from the cooperative action of hydrogen bonding and hydrophobic interactions is sensitive to both pH and temperature. The complexation preserves the micellar core-corona structure of the copolymer and shrinks the polyacid chains which adopt a compact structure. The non-dissociated polyacid sequences are bound to the PPO part of the copolymer forming the hydrophobic core of the complex, whereas the ionized polyacid sequences form with the PEO a stabilizing hydrated corona.Received: 27 April 2004, Published online: 3 August 2004PACS: 61.12.-q Neutron diffraction and scattering - 82.56.-b Nuclear magnetic resonance - 61.25.Hq Macromolecular and polymer solutions; polymer melts; swelling - 82.70.-y Disperse systems; complex fluids     

Dynamics of polaron in a polymer chain with impurities

In a polymer chain, an extra electron or hole distorts the chain to form a charged polaron, which is the charge carrier being responsible for conductivity. When an intermediate-strength electric field is applied, the polaron will be accelerated for a short time and then move at a constant velocity. The dynamical process of polaron in a polymer chain with impurities is simulated within a non-adiabatic evolution method, in which the electron wave function is described by the time-dependent Schrödinger equation while the polymer lattice is treated classically by a Newtonian equation of motion. We have considered two kinds of dynamical processes, one is the field-induced depinning of a charged polaron, which is initially bound by an attractive impurity; and the other is the scattering of a polaron from an impurity. In the former process, the charged polaron will depart from the attractive impurity only for the applied field with strength over a threshold, otherwise, the polaron will oscillate around the impurity. In the latter process, the charged polaron moves through the impurity in the presence of an electric field while it will be bounced back for a repulsive impurity or trapped to oscillate around an attractive impurity in the case that the applied electric field is weak and just be present for the polaron acceleration.Received: 4 June 2004, Published online: 14 December 2004PACS: 71.38.-k Polarons and electron-phonon interactions - 72.80.Le Polymers; organic compounds (including organic semiconductors)     

Conductance study of poly(ethylene oxide)- and poly(propylene oxide)-based polyelectrolytes

The ionic conductivity of poly(ethylene oxide) and poly(propylene oxide) in pure solution form, individually complexed with salts of Na⁺ and Li⁺, with and without plasticizer (propylene carbonate) and in blended form with individual salt with and without plasticizer, was studied. The conductance measurements were made at various concentrations of salt polymer complexes and at different temperatures. The effects of temperature and plasticizer concentration were measured from Arrhenius conductance plots. It is shown that the addition of salts in pure PEO increases conductance many times. The plasticizer has also same effect. The blending of PEO with PPO gives enhanced conductivity as compared to pure PEO. The activation energies were determined for all the systems which gave higher values for pure PEO and the value decreases with the addition of Li and Na salts and further decreases with the addition of plasticizer. The blending has also lowered the activation energy values which mean that incorporation of PPO in PEO has decreased crystallinity and the amorphous region has increased the local mobility of polymer chains resulting in lower activation energies.     

Inter-lamellar interactions modulated by addition of guest components

We have investigated the effects of a guest component (polymer or spherical colloidal particle) confined between flexible lamellar slits on the inter-lamellar interaction by means of a small-angle X-ray scattering technique and a neutron spin echo technique. The dominant interaction between flexible lamellar membranes without guest components is the Helfrich mechanism. The addition of a neutral polymer into the lamellar phase induces an attractive inter-lamellar interaction and finally destabilizes the lamellar phase. On the other hand, spherical colloidal particles confined between flexible lamellar membranes reduce the undulational fluctuations of lamellae and bring a repulsive inter-lamellar interaction. The behavior of the layer compression modulus of the lamellar membrane containing colloidal particles is well described by the entropical repulsive inter-lamellar interaction driven by steric hindrance.Received: 26 March 2004, Published online: 4 May 2004PACS: 82.70.Uv Surfactants, micellar solutions, vesicles, lamellae, amphiphilic systems, (hydrophilic and hydrophobic interactions) - 61.25.Hq Macromolecular and polymer solutions; polymer melts; swelling - 83.80.Hj Suspensions, dispersions, pastes, slurries, colloids - 89.75.Fb Structures and organization in complex systems     

Structural properties of charged diblock copolymer solutions

Aqueous micellar solutions of ionic/neutral block copolymers have been studied by light scattering, small angle neutron scattering and small angle X-ray scattering. We made use of a polymer comprised of a short hydrophobic block (polyethylene-propylene) PEP and of a long polyelectrolytic block (polystyrene-sulfonate) PSSNa which has been shown previously to micellize in water. The apparent polydispersity of these micelles is studied in detail, showing the existence of a few large aggregates coexisting with the population of micelles. Solutions of micelles are found to order above some threshold in polymer concentration. The order is liquid-like, as demonstrated by the evolution with concentration of the peak observed in the structure factor (), and the degree of order is found to be identical over a large range of concentrations (up to 20 wt%). Consistent values of the aggregation number of the micelles are found by independent methods. The effect of salt addition on the order is found to be weak. Received: 19 June 1997 / Received in final form: 4 September 1997 / Accepted: 9 October 1997     

Micelles of poly(isoprene-b-2-vinylpyridine-b-ethylene oxide) terpolymers in aqueous media and their interaction with surfactants

Well-defined poly(isoprene-b-2-vinylpyridine-b-ethylene oxide) (PI-P2VP-PEO) triblock terpolymers were synthesized by anionic polymerization high-vacuum techniques. The terpolymers formed spherical three-layer (onion-type) micelles in neutral and acidic pH aqueous media as evidenced by static and dynamic light scattering. In pure water, kinetically frozen micelles with a core composed of a soft PI inner part and a hard P2VP outer shell and protected by a neutral PEO corona were formed. In acidic media the core was formed by the soft PI hydrophobic segment, whereas the corona consisted of an inner cationic polyelectrolyte P2VPH⁺ part and an outer PEO shell. The aggregation numbers were found to be high in all cases, due to the high hydrophobicity of the core-forming blocks. In the latter case an increase in size was observed due to the electrostatic repulsions between the P2VPH⁺ chains in the inner part of the corona, which is also responsible for the lower aggregation numbers observed in the acidic solutions. The interaction of these onion-type micelles with cationic (DTMAB) and anionic (SDS) surfactants led to the formation of mixed polymer/surfactant aggregates. Their structural characteristics could be varied by combining changes in surfactant type and concentration, solution pH and type of electrostatic interaction, leading to interesting, block-copolymer-based, environmentally responsive colloidal systems.     

Microrheology and dynamics of an associative polymer

We study the microscopic viscoelastic properties and relaxation dynamics of solutions of a side-chain associative polymer, hydrophobically modified hydroxyethyl cellulose (hmHEC). Dynamic light scattering from small tracer particles suspended in the polymer solutions is used to determine their viscous and elastic moduli on the scale of the particles. Bulk-scale viscoelastic properties are measured by shear rheometry. The motion of the tracer particles in hmHEC is diffusive at short times and subdiffusive at intermediate and long times. The long-time subdiffusive motion was not observed in parallel experiments on unmodified HEC solutions, and is explained in terms of hindered reptation of the hydrophobically modified polymer chains in the associative network. Dynamic light scattering from the polymer molecules themselves shows that chain relaxation in hmHEC is dominated by slow concentration-dependent processes due to the large-scale associative network structure, while that in HEC is dominated by fast concentration-independent Rouse-like dynamics.