Adsorption of diblock copolymers on stripe-patterned surfaces

We present the results of extensive Monte Carlo simulations of diblock copolymers adsorbed on stripe-patterned surfaces of various widths. We have found that the width of the stripe pattern is an important parameter which dictates favorable recognition on the surface. For certain stripe widths, the adsorption of diblock copolymers to striped surfaces exhibits two transitions. The process involves recognition of the surface pattern by the diblock copolymer which follows a two step process in which the first block getting adsorbed to the appropriate pattern on the surface, without any recognition of the surface pattern, followed by the adsorption of the second block, where a reorganization process happens. For small widths and also for higher widths, the chain behaves just like a homopolymer where the twofold adsorbing process changes to the typical homopolymer adsorption. We have also found that there exists an optimal width of the stripes, independent of the chain length, where the recognition on the surface pattern is most favored. The characteristic temperature of the adsorption of the second block with weaker interactions is found to be independent of the chain length at this optimal width, proving that only local rearrangements take place after the first step. Some of our results describing the thermodynamics compare very well with the recent semianalytical approach of Kriksin et al. [J. Chem. Phys. 122, 114703 (2005)] on multiblock copolymers on heterogeneous surfaces. We also present some interesting conformational properties of the copolymer chain near the stripe-patterned surface.     

Adsorption and freezing of diblock copolymers on stripe-patterned surfaces: a scaling analysis

We present the results of scaling analysis of diblock copolymers adsorbed on stripe-patterned surfaces of various widths. Our previous studies [K. Sumithra and E. Straube, J. Chem. Phys. 125, 154701 (2006)] show that the adsorption of diblock copolymer on patterned surfaces yields two peaks in the specific heat capacity, thereby indicating two transition. In the current study, we characterize these two transitions. The scaling of the adsorption energy data proves that the first peak in the heat capacity curve is, in fact, associated with the adsorption transition. We found that for this transition the classical scaling laws are obeyed and that the critical crossover exponent is unaltered with respect to the case of homogeneous polymers. However, we found a change in the scaling exponent in the case of parallel component of the radius of gyration. It is evident from the scaling analysis of the parallel component of the radius of gyration that the chain is stretched along the direction of the stripes. The scaling plot shows, for (square root )/Nnu, an exponent of approximately 0.55 which is much different from that expected of a self-avoiding chain (nud=2-nu)/phi which is 0.25. The observed value is closer to an exponent of (nud=1-nu)/phi=0.69, for a completely stretched chain in one dimension. The perpendicular component of the radius of gyration shows deviation from the power law and the slope is steeper than the expected value of -2. We have also defined an order parameter to characterize the second transition and have found that it corresponds to a freezing transition where there are only a few dominant conformations. The perpendicular component of the radius of gyration also supports this information.     

Adsorption/desorption studies on nanocrystalline alumina surfaces

Two kinds of nanocrystalline alumina powders, boehmite (gamma-AlOOH, particle size d approximately 10 nm, BET surface area A(BET) = 180-200 m(2) g(-1)) and corundum (alpha-Al(2)O(3), d approximately 400 nm, A(BET) = 7 m(2) g(-1)) were used for comparative investigation by thermogravimetry (TG). The remarkable difference in the dehydration profiles between the two samples gives evidence for a distinct difference in their structures. In the following pyridine adsorption/desorption experiment, gamma-alumina was found to possess much more (20 times) and much stronger acidic sites than corundum. The activation energy of pyridine desorption was obtained from the respective minima in the first derivative of the TG-curves (DTG) at various heating rates (1-20 K min(-1)); the activation energy for pyridine desorption is smaller for gamma-alumina (61.5 kJ mol(-1)) than for corundum (78.8 kJ mol(-1)). Furthermore, the adsorption of water, carbon tetrachloride, and hexane on those alumina specimens provides evidence for the highly hydrophilic nature of their surfaces. The shift of T(max) to higher temperatures upon desorption of water was ascribed to the different adsorption coverage and the different energy required for removal of adsorbed water molecules.     

Adsorption of charged diblock copolymers on porous silica

Block copolymers of styrene and 2-vinylpyridine of different molecular weights were synthesized and chemically modified to poly(vinyl pyridine)/poly(styrene sulfonate) or polystyrene/poly(2-vinyl pyridinium) salts. Adsorption on “Spherosil” silica with a high specific surface area was performed from aqueous solutions of polyelectrolyte copolymers or from noncharged copolymer in an organic medium and subsequent sulfonation or quaternization in the adsorbed state. The adsorption mechanism was studied under various solvent conditions to give silica maximal ion-exchange properties. Modification of silica resulted in a highly stable coated material which combines the mechanical properties of the porous beads and the ion-exchange properties of the “supported” and “pellicular” ion-exchangers and should have potential use in chromatography.     

Strength and nature of hydrogen bonding interactions in mono- and di-hydrated formamide complexes

In this work, mono- and di-hydrated complexes of the formamide were studied. The calculations were performed at the MP2/6-311++G(d,p) level of approximation. The atoms in molecules theory (AIM), based on the topological properties of the electronic density distribution, was used to characterize the different types of bonds. The analysis of the hydrogen bonds (H-bonds) in the most stable mono- and di-hydrated formamide complexes shows a mutual reinforcement of the interactions, and some of these complexes can be considered as "bifunctional hydrogen bonding hydration complexes". In addition, we analyzed how the strength and the nature of the interactions, in mono-hydrated complexes, are modified by the presence of a second water molecule in di-hydrated formamide complexes. Structural changes, cooperativity, and electron density redistributions demonstrate that the H-bonds are stronger in the di-hydrated complexes than in the corresponding mono-hydrated complexes, wherein the σ- and π-electron delocalization were found. To explain the nature of such interactions, we carried out the atoms in molecules theory in conjunction with reduced variational space self-consistent field (RVS) decomposition analysis. On the basis of the local Virial theorem, the characteristics of the local electron energy density components at the bond critical points (BCPs) (the 1/4? (2)ρ(b) component of electron energy density and the kinetic energy density) were analyzed. These parameters were used in conjunction with the electron density and the Laplacian of the electron density to analyze the characteristics of the interactions. The analysis of the interaction energy components for the systems considered indicates that the strengthening of the hydrogen bonds is manifested by an increased contribution of the electrostatic energy component represented by the kinetic energy density at the BCP.     

Controlled supramolecular assembly of micelle-like gold nanoparticles in PS-b-P2VP diblock copolymers via hydrogen bonding

We report a facile strategy to synthesize amphiphilic gold (Au) nanoparticles functionalized with a multilayer, micelle-like structure consisting of a Au core, an inner hydroxylated polyisoprene (PIOH) layer, and an outer polystyrene shell (PS). Careful control of enthalpic interactions via a systematic variation of structural parameters, such as number of hydroxyl groups per ligand (N(OH)) and styrene repeating units (N(PS)) as well as areal chain density of ligands on the Au-core surface (Σ), enables precise control of the spatial distribution of these nanoparticles. This control was demonstrated in a lamellae-forming poly(styrene-b-2-vinylpyridine) (PS-b-P2VP) diblock copolymer matrix, where the favorable hydrogen-bonding interaction between hydroxyl groups in the PIOH inner shell and P2VP chains in the PS-b-P2VP diblock copolymer matrix, driving the nanoparticles to be segregated in P2VP domains, could be counter balanced by the enthalphic penalty of mixing of the PS outer brush with the P2VP domains. By varying N(OH), N(PS), and Σ, the nanoparticles could be positioned in the PS or P2VP domains or at the PS/P2VP interface. In addition, the effect of additives interfering with the hydrogen-bond formation between hydroxyl groups on Au nanoparticles and P2VP chains in a diblock copolymer matrix was investigated, and an interesting pea-pod-like segregation of Au nanoparticles in PS domains was observed.     

Adsorption of random copolymers on disordered surfaces

Monte Carlo simulations are used to study adsorption of random heteropolymers on disordered substrates. The adsorbent surface is modelled as an impenetrable wall with the random distribution of sites characterised by short-ranged segment-specific interactions with the polymer. Spatial fluctuations in the interaction strength are described as a Gaussian process with zero mean and variance σ₁ which is proportional to the site/segment potential, and to the loading of sites on the surface. In all cases, a moderate depletion in the polymer density is observed at small surface loading. Upon increasing σ₁ the polymer begins to adsorb on the surface. At a certain threshold loading, we observe a sharp second adsorption transition followed by gradual saturation. The transition is interpreted in terms of pattern matching; i.e. the heteropolymers accomodate themselves at surface domains with site distributions that match the configuration and the sequence of the chain when the sequence and surface site distributions are related in a special way. Distinct peaks in heat capacity and compressibility observed at the adsorption transition point to a first order process envisaged in earlier replica/mean-field analysis. These results suggest that random heteropolymers with designed sequence statistics can ‘recognise’ multifunctional disordered surfaces due to statistical pattern-matching.     

Adsorption characteristics of zwitterionic diblock copolymers at the silica/aqueous solution interface

The adsorption of a zwitterionic diblock copolymer, poly(2-(diethylamino)ethyl methacrylate)-block-poly(methacrylic acid) (PDEA59-PMAA50), at the silica/aqueous solution interface has been characterised as a function of pH. In acidic solution, this copolymer forms core-shell micelles with the neutral PMAA chains being located in the hydrophobic cores and the protonated PDEA chains forming the cationic micelle coronas. In alkaline solution, the copolymer forms the analogous inverted micelles with anionic PMAA coronas and hydrophobic PDEA cores. The morphology of the adsorbed layer was observed in situ using soft-contact atomic force microscopy (AFM): this technique suggests the formation of a thin adsorbed layer at pH 4 due to the adsorption of individual copolymer chains (unimers) rather than micelle aggregates. This is supported by the remarkably low dissipation values and the relatively low degrees of hydration for the adsorbed layers, as estimated using a combination of quartz crystal microbalance with dissipation monitoring (QCM-D) and optical reflectometry (OR). In alkaline solution, analysis of the adsorption data suggests a conformation for the adsorbed copolymers where one block projects normal to the solid/liquid interface; this layer consists of a hydrophobic PDEA anchor block adsorbed on the silica surface and an anionic PMAA buoy block extending into the solution phase. Tapping mode AFM studies were also carried out on the silica surfaces after removal from the copolymer solutions and subsequent drying. Interestingly, in these cases micelle-like surface aggregates were observed from both acidic and alkaline solutions. The lateral dimension of the aggregates seen is consistent with the corresponding hydrodynamic diameter of the copolymer micelles in bulk solution. The combination of the in situ and ex situ AFM data provides evidence that, for this copolymer, micelle aggregates are only seen in the ex situ dry state as a result of the substrate withdrawal and drying process. It remains unclear whether these aggregates are caused by micelle deposition at the surface during the substrate withdrawal from the solution or as a result of unimer rearrangements at the drying front as the liquid recedes from the surface.     

Adsorption behavior of PS‐PEO diblock copolymers on silver and alumina surfaces: A surface plasmon resonance study

In this work, the adsorption behavior at the silver/toluene and alumina/toluene interface of polystyrene–polyethylene oxide (PS‐PEO) diblock copolymers of various molecular weights was investigated by implementation of the surface plasmon resonance (SPR) technique. This was accomplished under a careful choice of experimental setup and the use of a suitable physical model for the interpretation of the experimental data. Comparison between polystyrene homopolymer and PS‐PEO diblock copolymer adsorption measurements indicate that PS‐PEO is anchored on the alumina surface via the PEO block, while on silver the copolymer is attached by various chain segments. The measured final adsorption amounts on alumina are typical of end‐attached polymeric brush formation while the dynamics of the adsorption process present two clearly different evolution regimes. This work provides insight into the many advantages of the use of the SPR technique as a valuable tool for similar surface studies. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1580–1591, 2006     

Adsorption of semiflexible block copolymers on homogeneous surfaces

We present the results of extensive numerical off-lattice Monte Carlo simulations of semiflexible block-copolymer chains adsorbed onto flat homogeneous surfaces. We have compared the behavior of several chain structures, such as homopolymers, diblocks, (A(alpha)B(alpha)) block copolymers, and random heteropolymers. In all the cases studied, we have found the adsorption process to be favored with an increase of the chain rigidity. Particularly, the adsorption of diblock structures becomes a two-step process characterized by two different adsorbing temperatures that depend on the chain stiffness kappa, the chain length N, and the adsorbing energies epsilon(A) and epsilon(B). This twofold adsorbing process changes to a single one for copolymers of reduced block size alpha. Each block of the stiff copolymer chain is found to satisfy the classical scaling laws for flexible chains, however, we found the scaling exponent phi to depend on the chain stiffness. The measurement of the radius of gyration exhibits a typical behavior of a polymer chain composed of Nl(p) blobs whose persistence length follows l(p) approximately (kappa/k(B)T)(0.5) for large stiff chains.     

Adsorption of model surfactantlike copolymers on nanopatterned surfaces

The adsorption of polymers, copolymers, surfactants, and biopolymers is often used to engineer surfaces. Towards improving our understanding of polymer adsorption we report simulation results for the adsorption of model copolymers, resembling surfactants, on nanoscale patterned hydrophobic surfaces at infinitely dilute concentrations. The surfactants are composed by a hydrophobic tail and a hydrophilic head. Surfactant adsorption on the hydrophobic surface occurs in the tail-down configuration in which the tail segments are in contact with the surface. We investigate how the presence of a solid hard mask, used to create the nanoscale pattern on the underlying hydrophobic surface, affects the surfactant adsorption. We find that surfactant adsorption on the underlying hydrophobic surface is prevented when the characteristic dimensions of the solid hard mask are less than twice the radius of gyration. We also show that details about mask-surfactant head effective interactions have the potential to alter the characteristics of adsorption. When the mask repels the head segments, the surfactants hardly adsorb on the underlying hydrophobic surface. When the mask strongly attracts the surfactant heads, the surfactants may preferentially adsorb on the mask rather than on the underlying hydrophobic surface. Under these latter circumstances the adsorbed surfactants in some cases assume a head-down configuration in which the head segments are in contact with the mask and the tail segments extend towards the bulk solution. We explain our results in terms of enthalpy and entropy of adsorption and discuss practical implications.     

Synthesis and thermal properties of diblock copolymers utilizing non-covalent interactions

Diblock copolymers of poly(styrene) and poly(ethylene oxide) were prepared utilizing a bisterpyridine ruthenium complex as non-covalent interaction for the connection of the two blocks. Apart from the synthesis and characterization of four metallo-supramolecular block copolymers, first studies on the thermal properties of the block copolymers have been performed. A complex crystallization behavior was observed and is described in a qualitative fashion. The influence of the metal complex on the thermal stability of the metallo-supramolecular block copolymers remains a question for further investigation.     

Ordering mechanism of asymmetric diblock copolymers confined between polymer-grafted surfaces

Using self-consistent-field calculation, we study the equilibrium morphology of asymmetric block copolymer melts between two brush-covered surfaces. We discuss systematically the morphologies formed as a function of the grafting density of brushes and show a series of reentrant structural transformations between the lamellar and hexagonal phases. Such a selection of ordered microdomains has been attributed to the interplay among entropy effects of stretched brushes, the preferential interaction of the blocks with the grafted substrate, and the bulk microphase-separated behavior of asymmetric copolymers. Interestingly for the affinitive brush-copolymer interfaces, the bulk hexagonal phase may still be remained due to entropy elasticity of brushes, and the frustration can be relieved by deforming the shape of "soft" polymer-brush surface, in contrast to the hard-wall cases. The result demonstrates a simple way to realize molecular self-assembly for confined copolymer films with well-controlled thickness and interfacial environment.     

Analytic density-functional self-consistent-field theory of diblock copolymers near patterned surfaces

Analytical solutions are derived for the density profiles and the free energies of compressible diblock copolymer melts (or incompressible copolymer solutions) near patterned surfaces. The density-functional self-consistent-field theory is employed along with a Gaussian chain model for bonding constraints and a random mixing approximation for nonbonded interactions. An analytical solution is rendered possible by expanding the chain distribution function around an inhomogeneous reference state with a nontrivial analytical solution, by retaining the linear terms, and by requiring consistency with the homopolymer limit. The density profiles are determined by both real and complex roots of a sixth-degree polynomial that may easily be obtained by solving a generalized eigenvalue problem. This analytical formulation enables one to efficiently explore the large nine-dimensional parameter space and can serve as a first approximation to computationally intensive studies with more detailed models. Illustrative computations are provided for uniform and patterned surfaces above the order-disorder transition. The results are consistent with the previous self-consistent-field calculations in that lamellar ordering appears near the surface above the order-disorder transition and the lamella order perpendicular or parallel to the surface depending on the commensurability between the periods of the surface pattern and the density oscillations.     

Adsorption of hydrogen on palladium nanoparticle surfaces

The behaviors of hydrogen (H) adsorbed on the palladium (Pd) nanoparticles (NPs) are examined with the modified analytic embedded‐atom method potentials and MORSE potentials. We study the effects of particle size and H coverage, and compare their adsorption properties of nanoparticle's facets with that of flat surfaces. We simulate the Pd truncated octahedron NPs with atoms from 38 to 2406 and the coverage of adsorbed H up to 1.0 monolayer (ML). Site preferences, adsorption geometries, adsorption energies, and bond lengths of H? Pd are calculated. We have also calculated the potential energy surface (PES). It is clear that the H atom binding to particle facets is quite stronger than that of flat surfaces when the particle size is smaller than 3.2 nm. We have found a significant variation that adsorption energies ascend gradually with increasing the particle size or surface coverage of H, and the adsorption energy varies about 0.6 eV for (111) facet and 0.3 eV for (100) facet as the coverage up to 1.0 ML. Our results are in reasonable agreement with the experimental values and other calculations. Copyright © 2009 John Wiley & Sons, Ltd.     

Adsorption of comb copolymers on weakly attractive solid surfaces

In this work continuum and lattice Monte Carlo simulation methods are used to study the adsorption of linear and comb polymers on flat surfaces. Selected polymer segments, located at the tips of the side chains in comb polymers or equally spaced along the linear polymers, are attracted to each other and to the surface via square-well potentials. The rest of the polymer segments are modeled as tangent hard spheres in the continuum model and as self-avoiding random walks in the lattice model. Results are presented in terms of segment-density profiles, distribution functions, and radii of gyration of the adsorbed polymers. At infinite dilution the presence of short side chains promotes the adsorption of polymers favoring both a decrease in the depletion-layer thickness and a spreading of the polymer molecule on the surface. The presence of long side chains favors the adsorption of polymers on the surface, but does not permit the spreading of the polymers. At finite concentration linear polymers and comb polymers with long side chains readily adsorb on the solid surface, while comb polymers with short side chains are unlikely to adsorb. The simple models of comb copolymers with short side chains used here show properties similar to those of associating polymers and of globular proteins in aqueous solutions, and can be used as a first approximation to investigate the mechanism of adsorption of proteins onto hydrophobic surfaces.     

Probing water interactions and vacancy production on gadolinia-doped ceria surfaces using electron stimulated desorption

Polycrystalline gadolinia-doped ceria (GDC) surfaces were studied using low-energy (5-400 eV) electron stimulated desorption (ESD). H(+), O(+), and H(3)O(+) were the primary cationic desorption products with H(+) as the dominant channel. H(+), H(3)O(+), and O(+) have a 22 eV threshold followed by a yield change around 40 eV. H(+) also has an additional yield change approximately 75 eV and O(+) has an additional change approximately 150 eV. The O(+) ESD yield change approximately 150 eV may indicate bond breaking of Gd-O and the involvement of oxygen vacancies. The H(+) and H(3)O(+) threshold data collectively indicate the presence of hydroxyl groups and chemisorbed water molecules on the GDC surfaces. ESD temperature dependence measurements show that the interaction of water with GDC surface defect sites, mainly oxygen vacancies, influences the desorption of H(+), O(+), and H(3)O(+). The temperature dependence of the O(+) ESD at 400 eV incident electron energy yields a 0.21 eV activation energy. This is close to the energy needed for oxygen vacancy production next to a pair of Ce(3+) on a CeO(2) surface. These results may indicate a correlation between the O(+) ESD yield and oxygen vacancy density on GDC surfaces and a potential correlation of O(+) ESD and GDC ionic conductivity.     

Micellar parameters of diblock copolymers and their interactions with ionic surfactants

The interactions of non-ionic amphiphilic diblock copolymer poly（oxyethylene/oxybutylene）(E₃₉B₁₈) with anionic surfactant sodium dodecyl sulphate（SDS） and cationic surfactant hexadecyltrimethylammonium bromide（CTAB） were studied by using various techniques such as surface tension,conductivity,steady-state fluorescence and dynamic light scattering.Surface tension measurements were used to determine the critical micelle concentration（CMC） and thereby the free energy of micellization(△G_mic),free energy of adsorption(△G_ads),surface excess concentration（Γ） and minimum area per molecule（A）.Conductivity measurements were used to determine the critical micelle concentration（CMC）,critical aggregation concentration（CAC）,polymer saturation point（PSP）,degree of ionization（α） and counter ion binding（β）. Dynamic light scattering experiments were performed to check the changes in physiochemical properties of the block copolymer micelles taken place due to the interactions of diblock copolymers with ionic surfactants.The ratio of the first and third vibronic peaks（I₁/I₃） indicated the polarity of the pyrene micro environment and was used for the detection of micelle as well as polymer-surfactant interactions.Aggregation number（N）,number of binding sites（n） and free energy of binding （△G_b） for pure surfactants as well as for polymer-surfactant mixed micellar systems were determined by the fluorescence quenching method.     

Interplay between anion-pi and hydrogen bonding interactions

The interplay between two important noncovalent interactions involving aromatic rings is studied by means of high level ab initio calculations. They demonstrate that synergistic effects are present in complexes where anion-pi and hydrogen bonding interactions coexist. These synergistic effects have been studied using the "atoms-in-molecules" theory and the Molecular Interaction Potential with polarization partition scheme. The present study examines how these two interactions mutually influence each other.     

Eutectic crystallization and hydrogen bonding interactions in polymer/surfactant blends

The unusual eutectic crystallization behavior in the poly(ε‐caprolactone) (PCL) and 3‐pentadecylphonel (PDP) binary blends was investigated by differential scanning calorimetry and Fourier transform infrared (FTIR) spectroscopy. A eutectic system was found with the eutectic composition at 60 wt % PDP and the eutectic melting temperature at 35 °C. The melting process of the blend at the eutectic composition was studied by in situ FTIR. The concurrence of the melting of PCL and PDP crystallites and the sequential formation of hydrogen bonding interaction between PDP molecules and PCL chains were traced. It was also found that a further increase in temperature above the eutectic melting temperature would impair the hydrogen bonding and increase the content of nonassociated phenol hydroxyl group. The semicrystalline morphology of blends affected by the composition was also investigated. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1015–1023, 2009