Phase separation and dewetting in polystyrene/poly(vinyl methyl ether) blend thin films in a wide thickness range

Phase separation and dewetting processes of blend thin films of polystyrene (PS) and poly(vinyl methyl ether) (PVME) in two phase region have been studied in a wide film thickness range from 65 μm to 42 nm (∼2.5R_g, R_g being radius of gyration of a polymer) using optical microscope (OM), atomic force microscope (AFM) and small-angle light scattering (LS). It was found that both phase separation and dewetting processes depend on the film thickness and were classified into four thickness regions. In the first region above ∼15 μm the spinodal decomposition (SD) type phase separation occurs in a similar manner to bulk and no dewetting is observed. This region can be regarded as bulk. In the second region between ∼15 and ∼1 μm, the SD type phase separation proceeds in the early stage while the characteristic wavelength of the SD decreases with the film thickness. In the late stage dewetting is induced by the phase separation. In the third region between ∼1 μm and ∼200 nm the dewetting is observed even in the early stage. The dewetting morphology is very irregular and no definite characteristic wavelength is observed. It is expected that the irregular morphology is induced by mixing up the characteristic wavelengths of the phase separation and the dewetting. In the fourth region below ∼200 nm the dewetting occurs after a long incubation time with a characteristic wavelength, which decreases with the film thickness. It is considered that the layered structure is formed in the thin film during the incubation period and triggers the dewetting through the capillary fluctuation mechanism or the composition fluctuation one.     

Composition effect on dewetting of ultrathin films of miscible polymer blend

Two kinds of dewetting and their transition induced by composition fluctuation due to different composition in blend [poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN)] films on SiO_x substrate at 145 °C have been studied by in-situ atomic force microscopy (AFM). The results showed that morphology and pathway of dewetting depended crucially on the composition. Possible reason is the variation in intensity of composition fluctuation resulted from the change of components in polymer blend. Based on the discussion of this fluctuation due to the composition gradient, parameter of U_q0/E, which describes the initial amplitude of the surface undulation and original thickness of film respectively, has been employed to distinguish the morphologies of spontaneous dewetting including bicontinuous structures and holes. Prior to the investigation of dewetting, it is confirmed that this blend is miscible at 145 °C using grazing incidence ultra small-angle X-ray scattering (GIUSAX).     

Patterning thin polymer films by surface-directed dewetting and pattern transfer

The pattern evolution processes of thin polystyrene (PS) film on chemically patterned substrates during dewetting have been investigated experimentally. The substrates have patterns of self-assembly monolayers produced by microcontact printing with octadecyltrichlorosilane. Optical microscopy and atomic force microscopy images reveal that ordered micrometer scale pattern can be created by surface direct dewetting. Various pattern sizes and pattern complexities can be achieved by controlling the experimental parameters. The dewetting pattern has been transferred to form PDMS stamp for soft lithography.     

Effect of hydrodynamics on dynamics of phase separation in polystyrene/poly(vinyl methyl ether) blend

Polystyrene/poly(vinyl methyl ether) (PS/PVME) phase diagram was assessed by rheological tools and by on-line microscopy observations both under quiescent and shear flow conditions. Shear flow was found to induce both mixing and demixing of the mixture depending on the amplitude of the imposed shear rate. Viscoelastic properties of PS/PVME blends were also measured under steady shear flow near the phase separation temperature. At lower shear rate, flow enhances concentration fluctuation and induces phase segregation. At high shear rate, flow suppresses fluctuations and the polymer mixture keeps its miscible state. Several rheological signatures of phase transition were found. In steady shear flow, a secondary plateau in viscosity was observed when the temperature was close to T_s whereas, at the start-up shear flow, transient shear stress showed a second overshoot after a few minutes of shearing.     

Incoherent neutron scattering study on the local dynamics in polystyrene and poly(vinyl methyl ether) blends

Neutron scattering study using the fixed elastic window technique is performed to investigate the effect of blending on the local dynamics of each component for polystyrene and poly(vinyl methyl ether) blends. The non-Gaussian scattering behavior observed above a certain temperature for the PVME component can be well explained by considering the rotational motions of methyl groups around O-CH₃ axis. The mean-square displacements of the vibrational motions were approximately proportional to absolute temperature below the glass transition temperature, which is a signature of harmonic oscillations, and were hardly affected by blending PS. On the other hand, the mean-square displacement of the PS component in the blend was almost the same as that of pure PS, while the non-Gaussian parameter for the former was much larger in comparison with that of the latter. Blending with PVME leads to a large increase in the dynamical heterogeneity for the PS component.     

Phase separation in polymer blend thin films studied by differential AC chip calorimetry

AC chip calorimetry is used to study the phase separation behavior of 100 nm thin poly(vinyl methyl ether)/poly(styrene) (PVME/PS) blend films. Using the on-chip heaters, very short (10 ms-10 s) temperature jumps into the temperature window of phase separation are applied, simulating laser heating induced patterning. These temperature pulses produce a measurable shift in the glass transition temperature, evidencing phase separation. The effect of pulse length and height on phase separation can be studied. The thus phase separated PVME/PS thin films remix rapidly, in contrast with measurements in bulk. AC chip calorimetry seems to be a more sensitive technique than atomic force microscopy to detect the early stages of phase separation in polymer blend thin films.     

Nanostructured polymer blend formed from poly(N-vinylpyrrolidone) and end-functional polystyrene

Phase structures of blends of poly(N-vinylpyrrolidone) (PVP) with SO₃H terminated polystyrene (PSS) were investigated. The PVP-PSS blends were macroscopically homogeneous, although the blends of PVP with polystyrene (PS) showed macroscopic phase separation. The PVP-PSS blends, however, showed two glass transitions indicating existence of two phases. Small-angle X-ray scattering measurements revealed the PVP-PSS blends formed mesomorphically ordered morphologies which change with variation of blend composition. The nano-organized phase separation in the PVP-PSS blends was caused due to hydrogen bonding of the PVP with the terminal SO₃H group of the PSS and repulsive interaction between PVP and main chain of the PSS.     

Phase separation induced ordered patterns in thin polymer blend films

Strategies for the utilization of phase separation to generate ordered pattern in polymer thin film are reviewed. First, the fundamental theory and factors influencing phase separation in polymer thin film are discussed. That is followed by a discussion of the formation of ordered patterns induced by phase separation in polymer thin films under the influence of a chemical heterogeneous substrate, convection or breath figures. The mechanisms and the conditions for well-ordered structures generated by phase separation are then discussed to show that multi-scaled/multi-component patterns, stimuli-responsive patterns may be developed by controlling the preparation conditions or exposing the sample to different environments more complex structures. Finally, applications of fabricated patterns in pattern generation and reproduction, antireflecting coating, catalysis, bio-chips and optoelectronics are also discussed.     

Spinodal decomposition as a probe to measure the effects on molecular motion in poly(styrene-co-acrylonitrile) and poly(methyl methacrylate) blends after mixing with a low molar mass liquid crystal or commercial lubricant

The effects on molecular motion observed through early stage phase separation via spinodal decomposition, in melt mixed poly(styrene-co-acrylonitrile) (SAN) containing 25% by weight of acrylonitrile (AN) and poly(methyl methacrylate) (PMMA) (20/80 wt%) blends after adding two low molar mass liquid crystals (CBC33 and CBC53) and two lubricants (GMS and zinc stearate) were investigated using light scattering techniques. The samples were assessed in terms of the apparent diffusion coefficient (D_app) obtained from observation of phase separation in the blends. The early stages of phase separation as observed by light scattering were dominated by diffusion processes and approximately conformed to the Cahn-Hilliard linearised theory. The major effect of liquid crystal (LC) was to increase the molecular mobility of the blends. The LC generally increased the Cahn-Hilliard apparent diffusion coefficient, D_app, of the blend when added with concentrations as low as 0.2 wt%. GMS and zinc stearate can also improve the mobility of the blend but to a lesser extent and the effect does not increase at higher concentration. On the other hand, the more LC added, the higher the mobility. In all systems the second derivative of the Gibbs free energy becomes zero at the same temperature. The improved mobilities therefore seem to arise from changes in dynamics rather than thermodynamic effects.     

The effects of flow on miscibility in a blend of polystyrene and poly(vinyl methyl ether)

Shear and extensional flows can have a significant effect on the miscibility for a blend of polystyrene with poly(vinyl methyl ether). The cloud point temperature in a planar stagnation flow is elevated by as much as 12 K; the magnitude depends on the extension rate, the strain, and the blend composition. Flow-induced miscibility is also observed in the shear flow between parallel plates which has been used to test smaller samples and to prepare solid samples for further characterization. At lower temperatures, as much as 30 K below the coexistence temperature, flow-induced phase separation occurs in both shear flow and extensional flows. The stress, rather than deformation rate, appears to be the most important parameter in flow-induced phase separation.     

Effect of shear memory on the coarsening behaviour of polystyrene and poly(vinyl methyl ether) blend

The effect of shear memory on the coarsening behaviour of polystyrene/poly(vinyl methyl ether) (PS/PVME) blend which shows a typical lower critical solution temperature (LCST)-type phase diagram has been thoroughly investigated for the near critical composition (PS/PVME=30/70) using a time-resolved light scattering technique. The measurements were carried out at 135 °C (20 °C above the quiescent cloud point) at two different directions, parallel and normal to the direction of flow. Different shear memories were generated in the melt using a simple shear apparatus of parallel plate geometry. The coarsening process was influenced to a great extent by the shear history of the blend over the time scale of the measurement. The average domain size of the dispersed particles obtained from the analysis of the light scattering data on the basis of Deby Bueche theory was found to be shear memory dependent. The coarsening process was elevated and suppressed at low and high shear memory, respectively. This behaviour was attributed to the shift of the cloud point observed under same values of shear rates. In addition, the coarsening behaviour of this blend was found to be flow direction independent due to the very high viscosity ratio of the blend, which led to in turn rather circular domains of PS in PVME matrix without any elongation or orientation in the direction of flow. Furthermore, the coarsening process for all the measured samples was followed the general power low, regardless the shear history and the flow direction of the blends. This result indicated that; the shear could only retard or elevate the rate of domain growth without any effect on the coarsening mechanism.     

Interaction between poly(vinyl pyridine) and poly(2,6-dimethyl-1,4-phenylene oxide): A copolymer blend miscibility study

The phase behavior of blends of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) with random copolymers of styrene and 2-vinyl pyridine, Poly(S-co-2VP), as well as with random copolymers of styrene and 4-vinyl pyridine, Poly(S-co-4VP), has been investigated in order to estimate the values of the Flory-Huggins parameters χPPO,2VP and χPPO,4VP between PPO and 2-vinyl pyridine, resp. 4-vinyl pyridine. Using previously estimated values for the Flory-Huggins parameters 0.09<χS,2VP<0.11 and 0.30<χS,4VP<0.35, together with the literature value of χS,PPO=−0.043, the phase behavior observed as a function of the copolymer composition results in 0.11≤χPPO,2VP≤0.12 and 0.46≤χPPO,4VP≤0.48. Insight in the interaction between PPO and poly(vinyl pyridine) is of considerable interest for several nanotechnology developments, since PPO is used to improve the mechanical properties of e.g. PS-block-P4VP nanorods.     

Phase separation structure in poly(vinyl alcohol)/silk fibroin blend films

Blend films of a commercial poly(vinyl alcohol) (a-PVA) derived from vinyl acetate and silk fibroin (SF) obtained from degummed silk were prepared by mixing the aqueous solutions of both samples. A plain weave structure was recognized only in the blend films, whereas no structure was found for the superimposed films of both samples. The phase separation structure of the blend films was examined by microscopic observations elongation, tensile tests, and IR measurements. The microphase separation region increased with increase in the degree of polymerization of the PVA. In the IR spectra of the blend films with high PVA contents cast under certain conditions, the absorption peak attributed to the cross-β-form conformation of SF appeared strongly. Gelatin, a water-soluble and natural polymer, was also used for comparison with SF. The ternary phase diagram in an a-PVA/gelatin/H₂O system was obtained experimentally and the critical point was used to estimate the interaction parameter between PVA and gelatin molecules. The phase separation structure and the interaction between PVA and SF molecules were also discussed taking into consideration the results of the a-PVA/gelatin system. © 1998 SCI.     

Transient currents in poly(vinyl alcohol)–poly(vinyl pyrrolidone) polymer blend films

Transient currents (charging and discharging currents) in poly(vinyl alcohol) (PVA)–poly(vinyl pyrrolidone) (PVP) polymer blend films were measured over the temperature range 30–150°C at field strengths of 2.32–23.2 × 10⁶ Vm^?1. Polymer films were prepared by the isothermal immersion technique. Activation energies were evaluated from quasi-steady-state currents. A single relaxation peak was observed both from isochronal currents and low frequency dielectric relaxation. Activation energies evaluated from these two methods are found to be in fairly good agreement. The polarization is considered to be due to space charge origin along with some contribution from dipolar groups. The maximum loss was observed in Sample I (PVA: PVP = 25:75), suggesting maximum heterogeneity in this blend ratio.     

Towards the simulation of poly(vinyl phenol)/poly(vinyl methyl ether) blends by atomistic molecular modelling

Molecular simulations of poly(vinyl phenol)/poly(vinyl methyl ether) (PVPh/PVME) blends were performed and their degree of miscibility evaluated as a preliminary step before orientation simulations. A minimum of three periodic boundary condition amorphous models was constructed and analysed in terms of solubility parameter, X-ray pattern, pair correlation function, hydrogen bond fraction and backbone conformation. The values obtained are consistent with miscibility of the systems, although it is suggested that the degree of mixing is not uniform for the different models.     

A comparison of atomic force microscope friction and phase imaging for the characterization of an immiscible polystyrene/poly(methyl methacrylate) blend film

Three different forms of atomic force microscope (AFM) measurement, topography, friction force and phase imaging, have been used to investigate the surface morphology and local composition of an immiscible polystyrene (PS)/poly(methyl methacrylate) (PMMA) blend film. This sample forms discrete, micron-size domains in a continuous matrix, which is attributed to the segregation of PMMA in PS. When the samples were imaged in air, contrast in friction and phase images was caused by variations in sample topography only. When the samples were imaged under water, however, both friction and phase imaging yielded non-topographic contrast between domains. We ascribe the contrast in both of these imaging modes to preferential softening of the hydrophilic, PMMA-rich domains and to stronger tip-sample adhesive forces, highlighting the AFM's utility for probing local elastic properties and for compositional mapping of soft polymer samples.     

Deformation studies of polystyrene/poly(vinyl methyl ether) blends by mechanical-vibrational spectroscopy

We have analyzed the deformation behavior of compatible and incompatible polystyrene (PS) and poly(vinyl methyl ether) (PVME) blends by a combination of mechanical and vibrational spectroscopy. Macroscopic properties and segmental orientation were found to be sensitive to molecular weight, strain rate, and temperature of measurement above the glass-transition temperature. Considerably different orientation functions were found for the PS and PVME components. For the experiments carried out above the T_g of the blends, the deformation behavior measured was consistent with expectations of a rubbery network.     

Annealing effects on thickness of polystyrene thin films as studied by neutron reflectivity

We performed neutron reflectivity measurements on deuterated polystyrene thin films supported on silicon substrate as a function of temperature. In order to see effects of annealing on the thickness, the films were annealed at 80 °C for 12 h and 135 °C for 12 h, termed weakly and strongly annealed films, respectively. One of the main purpose of this study is to see if the negative expansivity reported for very thin films [Phys. Rev. Lett. 71 (1993) 867] is caused by unrelaxed structure due to lack of annealing. It was found that the weakly annealed films show negative expansivity in the glassy state and it disappears for the strongly annealed films with thickness above about 90 Å. This suggests that the negative expansivity is due to the unrelaxed structure. In addition to this relaxation process, the thickness difference between the heating process and the cooling process suggests that there is another very slow relaxation process in thin films detectable at around 135 °C or about 32 °C above the glass transition temperature T_g. As a candidate for this slow process a sliding motion proposed by de Gennes is discussed.     

Phase separation of polystyrene-b-(ethylene-co-butylene)-b-styrene (SEBS) deposited on polystyrene thin films

Phase separation of a triblock copolymer, polystyrene-b-(ethylene-co-butylene)-b-styrene (SEBS) on the thin films of a homopolymer, polystyrene (PS), was studied by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The final morphology after phase separation was found to be greatly dependent on the relation between the molecular weight of the PS block and homo-PS. Dispersed spherical and worm-like micelles of SEBS were observed when the molecular weight of homo-PS is smaller than the PS block in SEBS, while large structures with inner micro-phase separation of SEBS was found when the molecular weight of homo-PS was much higher than that of the PS block. The origin of such a change in morphology is attributed to the difference of structure and interfacial tension at the interface between the matrix homo-PS and the PS block in SEBS triblock copolymer assembly.     

Protein separation by cellulose acetate/sulfonated poly(ether imide) blend ultrafiltration membranes

A process for purifying aqueous solutions containing macromolecular proteins such as bovine serum albumin (BSA), egg albumin (EA), pepsin, and trypsin has been investigated. Protein removal from food and biorelated industrial waste streams are gaining increased visibility due to environmental concern and saving precious materials. Ultrafiltration (UF) processes are largely being applied for protein separation from aqueous streams. In this work, an attempt has been made to separate the valuable proteins using cellulose acetate (CA)/sulfonated poly(ether imide) (SPEI) blend UF membranes prepared in the absence and presence of the additive, polyethyleneglycol (PEG600) in various compositions. The blend membranes were subjected to the determination of pore statistics and molecular weight cut‐off (MWCO). Porosity and pore size of the membranes increased with increasing concentrations of SPEI and PEG600 in the casting solution. Similarly, the MWCOs of the blend membranes ranged from 20 to greater than 69 kDa, depending on the various polymer blend compositions. Surface morphology of the blend membranes were analyzed using scanning electron microscopy. Studies were carried out to find the rejection and permeate flux of proteins. On increasing the concentration of SPEI and PEG600, the rejection of proteins is decreasing, whereas the permeate flux has an increasing trend. The effect of hydrophilicity of SPEI on fouling of protein for CA/SPEI blend membranes was also discussed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008