Star-Like Micelles with Star-Like Interactions: A quantitative Evaluation of Structure Factor and Phase Diagram

PEP-PEO block copolymer micelles offer the possibility to investigate phase behaviour and interactions of star polymers (ultra-soft colloids). A star-like architecture is achieved by an extremely asymmetric block ratio (1:20). Micellar functionality f can be smoothly varied by changing solvent composition (interfacial tension). Structure factors obtained by SANS can be quantitatively described in terms of an effective potential developed for star polymers. The experimental phase diagram reproduces to a high level of accuracy the predicted liquid/solid transition. Whereas for intermediate f a bcc phase is observed, for high f the formation of a fcc phase is preempted by glass formation.Comment: 5 pages, 4 figures, PRL in pres

Influence of long-range correlated quenched disorder on the adsorption of long flexible polymer chains on a wall

The process of adsorption on a planar wall of long-flexible polymer chains in the medium with quenched long-range correlated disorder is investigated. We focus on the case of correlations between defects or impurities that decay according to the power-low $x^{-a}$ for large distances $x$, where ${\bf x}=({\bf r},z)$. Field theoretical approach in $d=4-\epsilon$ and directly in $d=3$ dimensions up to one-loop order for the semi-infinite $|\phi|^4$ m-vector model (in the limit $m\to 0$) with a planar boundary is used. The whole set of surface critical exponents at the adsorption threshold $T=T_a$, which separates the nonadsorbed region from the adsorbed one is obtained. Moreover, we calculate the crossover critical exponent $\Phi$ and the set of exponents associated with them. We perform calculations in a double $\epsilon=4-d$ and $\delta=4-a$ expansion and also for a fixed dimension $d=3$, up to one-loop order for different values of the correlation parameter $2<a\le 3$. The obtained results indicate that for the systems with long-range correlated quenched disorder the new set of surface critical exponents arises. All the surface critical exponents depend on $a$. Hence, the presence of long-range correlated disorder influences the process of adsorption of long-flexible polymer chains on a wall in a significant way.Comment: 4 figures, 2 table

Muon spin rotation and neutron scattering study of the non-centrosymmetric tetragonal compound CeAuAl3

We have investigated the non-centrosymmetric tetragonal heavy-fermion compound CeAuAl3 using muon spin rotation (muSR), neutron diffraction (ND) and inelastic neutron scattering (INS) measurements. We have also revisited the magnetic, transport and thermal properties. The magnetic susceptibility reveals an antiferromagnetic transition at 1.1 K with a possibility of another magnetic transition near 0.18 K. The heat capacity shows a sharp lambda-type anomaly at 1.1 K in zero-filed, which broadens and moves to higher temperature in applied magnetic field. Our zero-field muSR and ND measurements confirm the existence of a long-range magnetic ground state below 1.2 K. Further the ND study reveals an incommensurate magnetic ordering with a magnetic propagation vector k = (0, 0, 0.52) and a spiral structure of Ce moments coupled ferromagnetically within the ab-plane. Our INS study reveals the presence of two well-defined crystal electric field (CEF) excitations at 5.1 meV and 24.6 meV in the paramagnetic phase of CeAuAl3 which can be explained on the basis of the CEF theory. Furthermore, low energy quasi-elastic excitations show a Gaussian line shape below 30 K compared to a Lorentzian line shape above 30 K, indicating a slowdown of spin fluctuation below 30 K. We have estimated a Kondo temperature of TK=3.5 K from the quasi-elastic linewidth, which is in good agreement with that estimated from the heat capacity. This study also indicates the absence of any CEF-phonon coupling unlike that observed in isostructural CeCuAl3. The CEF parameters, energy level scheme and their wave functions obtained from the analysis of INS data explain satisfactorily the single crystal susceptibility in the presence of two-ion anisotropic exchange interaction in CeAuAl3.Comment: 28 pages and 17 figure

Micellization of Sliding Polymer Surfactants

Following up a recent paper on grafted sliding polymer layers (Macromolecules 2005, 38, 1434-1441), we investigated the influence of the sliding degree of freedom on the self-assembly of sliding polymeric surfactants that can be obtained by complexation of polymers with cyclodextrins. In contrast to the micelles of quenched block copolymer surfactants, the free energy of micelles of sliding surfactants can have two minima: the first corresponding to small micelles with symmetric arm lengths, and the second corresponding to large micelles with asymmetric arm lengths. The relative sizes and concentrations of small and large micelles in the solution depend on the molecular parameters of the system. The appearance of small micelles drastically reduces the kinetic barrier signifying the fast formation of equilibrium micelles.Comment: Submitted to Macromolecule

The sustainable worldwide offshore wind energy potential: A systematic review

The offshore wind industry is expanding rapidly around the world due to several factors enabling this source of renewable energy. Stronger wind resources in offshore areas, lack of social and geographical constraints related to onshore wind power, the evolution of technology, and increasing demand for electricity in coastal regions as a result of a massive increase in population are some of the factors favoring the use of wind energy. The assessment of the potential global capacity that considers the different economic, environmental, and social factors and the dynamics of market, policy, and technology are vital for estimating the competitiveness of offshore wind energy in the future energy profile. There are several studies and technical reports that evaluate the potential of offshore wind energy in different countries or regions. They used a different source of data, metrics, and quantitative approaches in appraising the potential offshore wind power capacity and its cost efficiency. The critical factors that have been considered are geographical, technical, economic, environmental, and social and market elements. This paper provides a systematic review for analyzing the studies that address the potential offshore wind energy around the world and published during the 2000–2016 period. This study highlights the key criteria for assessing the potential for offshore wind energy deployment and the related tools and methods

Charge Ordering and Ferroelectricity in Half-doped Manganites

By means of density-functional simulations for half-doped manganites, such as pseudocubic Pr0.5Ca0.5MnO3 and bilayer PrCa2Mn2O7, we discuss the occurrence of ferroelectricity and we explore its crucial relation to the crystal structure and to peculiar charge/spin/orbital ordering effects. In pseudocubic Pr0.5Ca0.5MnO3, ferroelectricity is induced in the Zener polaron type structure, where Mn ions are dimerized. In marked contrast, in bilayer PrCa2Mn2O7, it is the displacements of apical oxygens bonded to either Mn3+ or Mn4+ ions that play a key role in the rising of ferroelectricity. Importantly, local dipoles due to apical oxygens are also intimately linked to charge and orbital ordering patterns in MnO2 planes, which in turn contribute to polarization. Finally, an important outcome of our work consists in proposing Born effective charges as a valid mean to quantify charge disproportionation effects, in terms of anisotropy and size of electronic clouds around Mn ions.Comment: 5 pages, 2 figures, submitted for publicatio

Critical behaviour of the Rouse model for gelling polymers

It is shown that the traditionally accepted "Rouse values" for the critical exponents at the gelation transition do not arise from the Rouse model for gelling polymers. The true critical behaviour of the Rouse model for gelling polymers is obtained from spectral properties of the connectivity matrix of the fractal clusters that are formed by the molecules. The required spectral properties are related to the return probability of a "blind ant"-random walk on the critical percolating cluster. The resulting scaling relations express the critical exponents of the shear-stress-relaxation function, and hence those of the shear viscosity and of the first normal stress coefficient, in terms of the spectral dimension $d_{s}$ of the critical percolating cluster and the exponents $\sigma$ and $\tau$ of the cluster-size distribution.Comment: 9 pages, slightly extended version, to appear in J. Phys.

Dragging a polymer chain into a nanotube and subsequent release

We present a scaling theory and Monte Carlo (MC) simulation results for a flexible polymer chain slowly dragged by one end into a nanotube. We also describe the situation when the completely confined chain is released and gradually leaves the tube. MC simulations were performed for a self-avoiding lattice model with a biased chain growth algorithm, the pruned-enriched Rosenbluth method. The nanotube is a long channel opened at one end and its diameter $D$ is much smaller than the size of the polymer coil in solution. We analyze the following characteristics as functions of the chain end position $x$ inside the tube: the free energy of confinement, the average end-to-end distance, the average number of imprisoned monomers, and the average stretching of the confined part of the chain for various values of $D$ and for the number of monomers in the chain, $N$. We show that when the chain end is dragged by a certain critical distance $x^*$ into the tube, the polymer undergoes a first-order phase transition whereby the remaining free tail is abruptly sucked into the tube. This is accompanied by jumps in the average size, the number of imprisoned segments, and in the average stretching parameter. The critical distance scales as $x^*\sim ND^{1-1/\nu}$. The transition takes place when approximately 3/4 of the chain units are dragged into the tube. The theory presented is based on constructing the Landau free energy as a function of an order parameter that provides a complete description of equilibrium and metastable states. We argue that if the trapped chain is released with all monomers allowed to fluctuate, the reverse process in which the chain leaves the confinement occurs smoothly without any jumps. Finally, we apply the theory to estimate the lifetime of confined DNA in metastable states in nanotubes.Comment: 13pages, 14figure

Interactions between proteins bound to biomembranes

We study a physical model for the interaction between general inclusions bound to fluid membranes that possess finite tension, as well as the usual bending rigidity. We are motivated by an interest in proteins bound to cell membranes that apply forces to these membranes, due to either entropic or direct chemical interactions. We find an exact analytic solution for the repulsive interaction between two similar circularly symmetric inclusions. This repulsion extends over length scales of order tens of nanometers, and contrasts with the membrane-mediated contact attraction for similar inclusions on tensionless membranes. For non circularly symmetric inclusions we study the small, algebraically long-ranged, attractive contribution to the force that arises. We discuss the relevance of our results to biological phenomena, such as the budding of caveolae from cell membranes and the striations that are observed on their coats.Comment: 22 pages, 2 figure

Theta-point universality of polyampholytes with screened interactions

By an efficient algorithm we evaluate exactly the disorder-averaged statistics of globally neutral self-avoiding chains with quenched random charge $q_i=\pm 1$ in monomer i and nearest neighbor interactions $\propto q_i q_j$ on square (22 monomers) and cubic (16 monomers) lattices. At the theta transition in 2D, radius of gyration, entropic and crossover exponents are well compatible with the universality class of the corresponding transition of homopolymers. Further strong indication of such class comes from direct comparison with the corresponding annealed problem. In 3D classical exponents are recovered. The percentage of charge sequences leading to folding in a unique ground state approaches zero exponentially with the chain length.Comment: 15 REVTEX pages. 4 eps-figures . 1 tabl