Fabrication of a gradient heterogeneous surface using homopolymers and diblock copolymers

The strength of the interfacial interactions and the length scale over which these interactions occur are key factors in understanding the thin film behavior of polymer blends and diblock copolymers, adhesion, wettability, and recognition processes of cells and random heteropolymers on surfaces. Here, gradient heterogeneous surface topographies were prepared using thin films of mixtures of homopolymers and diblock copolymers to vary the lateral size scale of heterogeneities from the microscopic to nanoscopic. Dewetting, phase separation, and cell adhesion were used to demonstrate the utility of these surfaces having gradient heterogeneous topographies. By tuning the lateral size scale of the heterogeneities, surface patterns can be engineered to meet a specific function. Gradient surfaces offer a straightforward method to optimize various length scales of heterogeneity.     

Styrene-methyl acrylate copolymers and acrylate homopolymers in solution

Molecular weight determinations by light scattering and osmometry and intrinsic viscosity measurements were made in various solvents on fractions of styrene–methyl acrylate copolymers with different compositions and on acrylate homopolymers prepared by free-radical reaction. Relations between intrinsic viscosity [η] and molecular weight M thus established are compared with those reported by other authors. 2-Methylcyclohexanol was found to be a theta solvent for the copolymers and both parent homopolymers, and isoamyl acetate was a theta solvent for poly(methyl acrylate). From theta point viscosity data obtained with these solvents, unperturbed chain dimensions were estimated. The results are compared with the unperturbed dimensions estimated from the [η]–M relations obtained in good solvents. On the basis of the experimental data it was found that the unperturbed dimension depends linearly on the copolymer composition, in contrast to the case of styrene–methyl methacrylate copolymers. Composition dependences of the theta temperature and of the parameter describing the long-range interactions between nonadjacent segments in polymer chains were investigated. The result implies that long-range interactions between monomeric units never disappear even when those between the same monomeric units vanish. The Huggins constant for copolymer is discussed in terms of the excluded volume variable.     

Matched ring diblock and linear triblock copolymers in dilute solution

A unique diblock copolymer ring and its linear triblock copolymer precursor composed of polystyrene and polydimethylsiloxane have been characterized by static and dynamic light scattering in dilute solution. The measurements were carried out with cyclohexane as the solvent over a temperature range of 12–35°C. Cyclohexane has the useful property that it is nearly isorefractive with the PDMS so that the PDMS block segments are invisible to the light-scattering technique and it is a theta solvent for polystyrene at 34.5°C. The block polymers in this work contain 35.1 wt % of styrene as determined by proton NMR. In the linear triblock polymer, the polystyrene is the center block with PDMS blocks on each side. Static light scattering measurements give 4.31 × 10⁴ for the average molecular weight of the whole polymer. Light scattering also shows that the apparent theta temperature for the linear triblock is shifted by 15°C to a value of 20°C at which point the second virial coefficient drops sharply and phase separation begins to induce aggregation. The diblock ring, however, shows a strongly positive second virial coefficient and no aggregation even at 12°C which is the limit of these experiments. The diffusion coefficients of cyclic diblock (D_c) and linear triblock copolymer (D₁) are measured by dynamic light scattering. The ratio of diffusion coefficients of cyclic and linear copolymers at 14.9°C and 30°C are D_c/D_l = 1.13 and 1.107 respectively. These compare well with prediction of 1.18 for this ratio from consideration of the hydrodynamics of matched linear and cyclic polymer chains. Dynamic light scattering quantitatively confirms that the linear copolymer experiences a solvent quality change near 20°C but the cyclic polymer remains in good solvent over the entire experimental temperature range. © 1993 John Wiley & Sons, Inc.     

Simulated annealing study of morphological transitions of diblock copolymers in solution

The simulated annealing method was applied to study the self-assembling process of diblock copolymers in selective solvents for one block. The simulation results illustrated that the morphologies of the copolymer aggregates strongly depend on the interactions between the core-forming blocks and the solvents and on the length of the corona-forming blocks. Multiple morphological transitions were observed in one system. The transition sequence (disordered state-spherical micelles-short rodlike micelles-long rodlike micelles-onionlike aggregates) was observed for copolymers with increasing core-solvent interaction. Similar transitions were observed with the decrease of the length of the corona-forming blocks. The mechanisms of these transitions are investigated. The simulation results are compared with experiments and other simulations.     

Shear induced mixing/demixing: blends of homopolymers,of homopolymers plus copolymers,and blends in solution

Shear may shift the phase boundary towards the homogeneous state (shear induced mixing, SIM), or in the opposite direction (shear induced demixing, SID). SIM is the typical behavior of mixtures of components of low molar mass and polymer solutions, SID can be observed with solutions of high molar mass polymers and polymer blends at higher shear rates. The typical sequence with increasing shear rate is SIM, then occurrence of an isolated additional immiscible area (SID), melting of this island into the main miscibility gap, and finally SIM again. A three phase line originates and ends in two critical end points. Raising pressure increases the shear effects. For copolymer containing systems SID is sometimes observed at very low shear rates, preceding the just mentioned sequence of shear influences.     

Structure of polypeptide-based diblock copolymers in solution: stimuli-responsive vesicles and micelles

Polypeptide-based diblock copolymers forming either well-defined self-assembled micelles or vesicles after direct dissolution in water or in dichloromethane have been studied combining light and neutron scattering with electron microscopy experiments. The size of these structures could be reversibly manipulated as a function of environmental changes such as pH and ionic strength in water. Compared to other pH-responsive self-assembled systems based on "classical" polyelectrolytes, these polypeptide-based nanostructures present the ability to give a response in highly salted media as the chain conformational ordering can be controlled. This makes these micelles and vesicles suitable for biological applications: they provide significant advantages in the control of the structure and function of supramolecular self-assemblies.     

Orientation fluctuations in diblock copolymers

Depolarized light scattering and dielectric relaxation spectroscopy reveal pertinent composition fluctuations effects on the orientation dynamics in diblock copolymers near the ordering transition (ODT). The main evidence stems from the broadening of the block relaxation function and collective chain orientation in the disordered state near ODT as well as a slow relaxation process below ODT.     

Thermodynamic interactions of water-soluble homopolymers and double-hydrophilic diblock copolymer

Thermodynamic interaction parameters of water-soluble poly[2-(dimethylamino)ethyl methacrylate] (DMA) and poly[2-(N-morpholino)ethyl methacrylate] (MEMA) homopolymers and their diblock copolymer (DMA–MEMA) were investigated at the temperatures above their glass-transition temperatures (T_g) by inverse gas chromatography (IGC) method. Sorption thermodynamic parameters of some aliphatic, alicyclic and aromatic hydrocarbons, weight fraction activity coefficients, Flory–Huggins interaction parameters, and solubility parameters for hydrocarbons and polymers were calculated. It was observed that sorption thermodynamic parameters on (co)polymers depend on the molecular structures of hydrocarbons. Evaluating both the calculated values of the weight fraction activity coefficients and Flory–Huggins interaction parameters, the solving ability of the hydrocarbons for DMA, MEMA homopolymers, and DMA–MEMA diblock copolymer decreased in the following sequence: Aromatic > alicyclic > aliphatic hydrocarbons.     

Dynamic properties of microemulsions modified with homopolymers and diblock copolymers: the determination of bending moduli and renormalization effects

The properties of bicontinuous microemulsions, consisting of water, oil, and a surfactant, can be modified by the addition of diblock copolymers (boosting effect) and homopolymers (inverse boosting effect) or a combination of both. Here, the influence of the addition of homopolymers (PEP(X) and PEO(X), X=5k or 10k molecular weight) on the dynamics of the surfactant layer is studied with neutron spin echo spectroscopy (NSE). Combining the results with the previous findings for diblock copolymers allows for a better separation of viscosity and bending modulus effects. With the addition of homopolymers, a significant increase of the relaxation rate compared to the pure microemulsion has been observed. The influence on the bending rigidity kappa is measured with NSE experiments. Homopolymer addition reduces kappa by up to Deltakappa approximately -0.5k(B)T, whereas the diblock copolymer yields an increase of kappa by approximately 0.3k(B)T. Comparison of the bending moduli that are obtained by analysis of the dynamics to those obtained from small angle neutron scattering (SANS) sheds light on the different renormalization length scales for NSE and SANS. Variation of the surfactant concentration at otherwise constant conditions of homopolymer or diblock-copolymer concentration shows that NSE results are leading to the pure bending rigidity, while the renormalized one is measured with SANS.     

Synthesis and self‐assembly of thymine‐ and adenine‐containing homopolymers and diblock copolymers

Atom transfer radical polymerizations (ATRPs) of 1‐(4‐methacryloyloxy‐benzyl)thymine (MAT) and 9‐(2‐methacryloyloxyethyl)adenine (MAA) were conducted for the synthesis of DNA‐base functionalized polymers. The association equilibrium constant K_asso between MAT and MAA and the complexation equilibrium constant K_comp between the corresponding polymers PMAT and PMAA were determined. A zipper‐like diblock copolymer, PMAT‐b‐PMAA, was prepared by anchoring the PMAT and PMAA blocks on the ortho‐positions of a pyridine ring via a successive two‐step ATRP. Dynamic light scattering and atom force microscopy confirmed that the block copolymer had a V‐shaped configuration in dimethylsulfoxide/N,N‐dimethylformamide. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5995–6006, 2006     

Organogermane homopolymers and copolymers with organosilane

The first high molecular weight soluble, formable organogermane homopolymer (n-Bu₂Ge)_n was synthesized by the sodium coupling of n-Bu₂GeCl₂ in toluene. Soluble organogermane/organosilane copolymers [(X₂Ge)_x(YZSi)_y]_n were prepared by sodium coupling of X₂GeCl₂ and YZSiCl₂ in different molar ratios (X = n-bu, Ph; Y = n-hexyl, cyclohexyl; Z = Me). Germanium-containing polymers and copolymers with organosilanes are highly absorbing between 300–360 nm, with the absorption maxima dependent on the nature of the substituent and the ratio of X₂Ge:YZSi in the polymer. These polymers are photoactive and display bleaching behavior with photoscission.     

Aggregates in solution of binary mixtures of amphiphilic diblock copolymers with different chain length

The polydispersity effect of amphiphilic AB diblock copolymers on the self-assembled morphologies in solution has been investigated by the real-space implementation of self-consistent field theory (SCFT) in two dimensions (2D). The polydispersity is artificially obtained by mixing binary diblock copolymers where the hydrophilic or hydrophobic blocks are composed of two different lengths while the other block length is kept the same. The main advantage is that this simple polydispersity can easily distinguish the difference of aggregates in the density distribution of long and short block length intuitionally and quantitatively. The morphology transition from vesicles to micelles is observed with increasing polydispersity of copolymers due to the length segregation of copolymers. For polydisperse hydrophilic or hydrophobic blocks, the short blocks tend to distribute at the interfaces between hydrophilic and hydrophobic blocks while the long blocks stretch to the outer space. More specifically, by quantitatively taking the sum of all the concentration distribution of long and short chains over the inside and outside surface areas of the vesicle, it is found that long blocks prefer to locate on the outside surface of the vesicle while short ones prefer the inside. Such length segregation leads to large curvature of the aggregate, thus resulting in the decrease of the aggregate size.     

Probe diffusion in homogeneous diblock copolymers

Forced Rayleigh scattering was used to investigate the diffusion of a photoreactive dye molecule in two homogeneous poly(styrene-b-isoprene) (SI) diblock copolymers with overall molecular weights of approximately 2000. Although diffusion rates were intermediate to TTI transport in homopolymer polystyrene (PS) and polyisoprene (PI), system dynamics appear to be largely dictated in each case by the PI block. The size of the polymer jumping unit, on the other hand, is evaluated from a free-volume analysis of the data, and is found to be governed predominantly by the PS component of the copolymer. The mechanism for tracer diffusion in low-molecular-weight block copolymers appears analogous to transport in a high molecular weight SI diblock copolymer (M_n = 13,600) that has been solvated sufficiently in toluene to be microstructurally disordered. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1739–1746, 1998     

Phase separation in blends of two homopolymers and a diblock copolymer during film casting

Demixing during film casting of blends of polystyrene, polymethylmethacrylate, and a symmetric diblock copolymer of styrene and methylmethacrylate is discussed. The concentration fluctuations in the homogeneous solutions were calculated in mean field approximation. The structures in the homogeneous and demixed solutions and in the dry films were measured by small-angle x-ray scattering, and the morphologies of the dry films were characterized by transmission electron microscopy. The structure of the dry blends is evidently already pre-formed in solution.     

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.     

Features of structural relaxation in diblock copolymers

Time- and temperature-dependent structural relaxation (physical aging) of poly (styrene-b-methyl methacrylate) (PS-b-PMMA) block copolymers was investigated by calorimetry. Our study reveals the interplay of the relaxation responses of the two components of the copolymer in an intermediate temperature regime. That is, when the testing temperature is closely below the glass transition temperatures of PS and PMMA, structural relaxation in these polymer phases takes place concurrently, the corresponding thermogram displays partially superposed dual endothermic peaks as a feature of physical aging in the diblock copolymers. The aging response for each component is identified from a curve fitting method and analyzed by the relaxation of enthalpy. Comparing with the homopolymer analogs, the PS and PMMA in diblock copolymers show enhanced aging rate.     

Orientational ordering of nanorods in diblock copolymers

ABSTRACT

Orientational ordering of rod-like nanoparticles in the lamellae phase of diblock copolymers has been considered theoretically using the model of a nanoparticle with two interaction centres. It has been shown that strongly anisotropic nanoparticles order spontaneously in the boundary region between the blocks where the orientational order is induced by the interface and by the interaction with monomer units in different blocks. The nematic order parameter possesses opposite signs in adjacent blocks which means that the nanorods are aligned parallel or perpendicular to the boundary between the blocks on different sides of their interface. Concentration and nematic order parameter profiles have been calculated numerically for different values of the nanoparticle length and compared with the results of recent computer simulations and with the results of the previous molecular theory based on nanoparticles of spherical shape.     

Aggregates of rod-coil diblock copolymers adsorbed at a surface

The behavior of rod-coil diblock copolymers close to a surface is discussed by using extended scaling methods. The copolymers are immersed in selective solvent such that the rods are likely to aggregate to gain energy. The rods are assumed to align only parallel to each other, such that they gain a maximum energy by forming liquid crystalline structures. If an aggregate of these copolymers adsorbs with the rods parallel to the surface the rods shift with respect to each other to allow for the chains to gain entropy. It is shown that this shift decays with increasing distance from the surface. The profile of this decay away from the surface is calculated by minimization of the total free energy of the system. The stability of such an adsorbed aggregate and other possible configurations are discussed as well.