Water, salt water, and alkaline solution uptake in epoxy thin films

As a means of characterizing the diffusion parameters of fiber reinforced polymer (FRP) composites within a relatively short time frame, the potential use of short term tests on epoxy films to predict the long-term behavior is investigated. Reference is made to the literature to assess the effectiveness of Fickian and anomalous diffusion models to describe solution uptake in epoxies. The influence of differing exposure conditions on the diffusion in epoxies, in particular the effect of solution type and temperature, are explored. Experimental results, where the solution uptake in desiccated (D) or undesiccated (U) thin films of a commercially available epoxy matrix subjected to water (W), salt water (SW), or alkali concrete pore solution (CPS) at either 20 or 60°C, are also presented. It was found that the type of solution did not significantly influence the diffusion behavior at 20°C and that the mass uptake profile was anomalous. Exposure to 60°C accelerated the initial diffusion behavior and appeared to raise the level of saturation. In spite of the accelerated approach, conclusive values of uptake at saturation remained elusive even at an exposure period of 5 years. This finding questions the viability of using short-term thin film results to predict the long-term mechanical performance of FRP materials. © 2013 Wiley Periodicals, Inc.

Evolution of vertical phase separation in P3HT:PCBM thin films induced by thermal annealing

The achievement of the desirable morphology at the nanometer scale of bulk heterojunctions consisting of a conjugated polymer with fullerene derivatives is a prerequisite in order to optimize the power conversion efficiency of organic solar cells. The various experimental conditions such as the choice of solvent, drying rates and annealing have been found to significantly affect the blend morphology and the final performance of the photovoltaic device. In this work, we focus on the effects of post deposition thermal annealing at 140 °C on the blend morphology, the optical and structural properties of bulk heterojunctions that consist of poly(3-hexylthiophene) (P3HT) and a methanofullerene derivative (PCBM). The post thermal annealing modifies the distribution of the P3HT and the PCBM inside the blend films, as it has been found by Spectroscopic Ellipsometry studies in the visible to far-ultraviolet spectral range. Phase separation was identified by AFM and GIXRD as a result of a slow drying process which took place after the spin coating process. The increase of the annealing time resulted to a significant increase of the P3HT crystallinity at the top regions of the blend films. © 2011 Elsevier B.V. All rights reserved.

Thermal annealing effect on the nanomechanical properties and structure of P3HT:PCBM thin films

Nanostructured polymer-fullerene thin films are among the most prominent materials for application in high efficient polymer solar cells. Specifically, poly(3-hexylthiophene) (P3HT) and fullerene derivatives (PCBM) blends are used as the donor/acceptor materials forming a bulk heterojunction. Although P3HT:PCBM properties have been extensively studied, less light has been set on its nanomechanical properties, which affect the device service life. In this work Atomic Force Acoustic Microscopy (AFAM), Atomic Force Spectroscopy and Nanoindentation were used to study the effect of the fullerene presence and the annealing on the P3HT:PCBM nanomechanical behavior. The P3HT:PCBM thin films were prepared by spin coating on glass substrates and then annealed at 100 °C and 145 °C for 30 min. Large phase separation was identified by optical and Atomic Force Microscopy (AFM) for the annealed samples. Needle-like PCBM crystals were formed and an increase of the polymer crystallinity degree with the increase of the annealing temperature was confirmed by X-ray diffraction. AFAM characterization revealed the presence of aggregates close to stiff PCBM crystals, possibly consisting of amorphous P3HT material. AFM force-distance curves showed a continuous change in stiffness in the vicinity of the PCBM crystals, due to the PCBM depletion near its crystals, and the AFM indentation provided qualitative results about the changes in P3HT nanomechanical response after annealing. © 2011 Elsevier B.V. All rights reserved.

Picosecond laser patterning of PEDOT:PSS thin films

Picosecond pulsed laser (10.4 ps, 1064 nm, 5 and 50 kHz) patterning studies were performed, of PEDOT:PSS thin films of varying thickness deposited by spin coating on glass substrates, by ablating the films or by changing locally by laser irradiation the optical and electrical properties of the polymer. From a detailed observation of the morphology of single pulse ablated holes on the surfaces of the films, in combination with simple calculations, it is concluded that photomechanical ablation is the likely ablation mechanism of the films. The single pulse ablation thresholds were measured equal to 0.13-0.18 J/cm 2 for films with thicknesses in the region of ∼100-600 nm. The implications on ablation line patterning of the films using different fluences, scanning speeds and pulse repetition rates, were investigated systematically. Laser irradiation of the films before ablation induces a metal-insulator transition of the polymer because of the formation of charge localization due to a possible creation of molecular disorder in the polymer and shortening of its conjugation length. © 2010 Elsevier B.V. All rights reserved.

Investigation on the nonlinear optical properties of the DCNP/PEK-c guest-host polymer films

The polyetherketone (PEK-c) guest-host polymer thin films doped with 3-(1,1-dicyanothenyl)-1-phenyl-4,5-dihydro-1H-pryazole (DCNP) were prepared. The polymer films were investigated with in situ second-harmonic generation (SHG) measurement. The corona poling temperature was optimized by the temperature dependence of the in situ SHG signal intensity under the poling electric field applying. The temporal and temperature stability of the second-order properties of the poled polymer film were measured by the in situ SHG signal intensity probing. The second-order NLO coefficient chi ((2))(33) = 32.65 pm/V at lambda = 1064 nm was determined by using the Makel fringe method after poling under the optimal poling condition. The dispersion of the NLO coefficient of the guest-host polymer system was determined by the measured value of chi ((2))(33) at 1064 nm and the two-level model.

Electro-optical properties and temporal stability of the guest-host DCNP/PEK-c polymer thin film

The polyetherketone (PEK-c) guest-host system thin films in which the range of the weight percent of 3-(1,1-dicyanothenyl)-1-phenyl-4, 5- dihydro-1H-pryazole (DCNP) is from 20% to 50% were prepared. The predicted high value of electro-optical (EO) coefficient gamma(33) = 48.8 pm/V by using two-level model was obtained when the weight percent of DCNP in the polymer system is 40%, whereas EO coefficients are attenuated at higher chromophore loading then 40%. The temporal stability of the EO activity of the guest-host polymer was evaluated by probing the decay of the orientational order of the chromophores in the polymer system.

The dewetting dynamics of the polymer thin film by solvent annealing

The slippage effect of the polymer chains is investigated in the dewetting process of the polymer solution film. The solvent-induced dewetting is used in our experiments to study the dynamics of hole growth in the dewetting process of the polymer solution film. Our results show that in the case of the low molecular weight polystyrene (PS) film, the slippage effect of the polymer chains is not displayed and the radius of the holes is R similar to exp(t/tau); in the case of the higher molecular weight PS film, the slippage effect of the polymer chain is not valid in the case of the thin film and that is valid in the case of the thick film, and the dynamic process of hole growth divides into three stages (R similar to t, and then R similar to t(x) (2/3 < x < 1), finally, R similar to t). Besides, the solvent and substrate properties also influence the dewetting dynamics of the polymer solution film.

Single mode and multimodes lasing emission from MEH-PPV doped polystyrene thin films with surface ripples formed by vapour-induced phase separation

We report single mode and multimodes lasing emission from conjugated polymer poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) doped polystyrene ( PS) thin films with surface ripples. Surface ripples were formed by water vapour-induced phase separation. A single mode lasing emission at 606 nm with a line-width of less than 0.4 nm was obtained. The laser threshold was as low as 3.5 mu J pulse(-1). The side mode suppression ratio was 5.76 dB. The periodic changes of the refraction index in the MEH-PPV : PS blending film due to the phase separation should be attributed to the lasing actions.

Dendritic Superstructures and Structure Transitions of Asymmetric Poly(L-lactide-b-ethylene oxide) Diblock Copolymer Thin films

The evolution of morphologies of isothermally crystallized thin films with different thicknesses of poly(L-lactide-bethylene oxide) diblock copolymer was observed by optical microscopy (OM) and atomic force microscopy (AFM). Dendritic superstructures stacked with lamellae were investigated in thin films with similar to 200 nm to similar to 400 nm thickness. The lamellar structure was a lozenge- or truncated-lozenge-shaped single crystal of PLLA confirmed by AFM observations. The contour of the dendritic superstructures is hexagonal, and two types of sectors, [110] and [100], can be classified in terms of the chain-folding and crystal growth directions. These phenomena Are due to the interplay of the crystallization of the PLLA block, the microphase separation of the block copolymer, and the effect of the film thickness.

Microphase-Separated Brushes on Square Platelets in PS-b-PEO Thin Films

In polystyrene-block-poly(ethylene oxide) thin square platelets can be obtained via fast solvent evaporation by controlling the tethering density (0.08 < sigma < 0.11). The tethering density of the brushes is proportional to the thickness of the PEO crystal and increases with increasing initial solution heating temperature (T-i). When T-i < T-m, where T-m is the melting point of PEO, brushes with microphase-separated structures are observed. The formation of microphase-separated brushes depends on two factors: the strong incompatibility between PS and noncrystalline PEO chains (attached to the crystalline PEO) and the weak interaction between PS-PS brushes.

Lamella reorientation in thin films of a symmetric poly(L-lactic acid)-block-polystyrene upon crystallization at different temperatures

The thin films of a symmetric crystalline-coil diblock copolymer of poly(L-lactic acid) and polystyrene (PLLA-b-PS) formed lamellae parallel to the substrate surface in melt. When annealed at temperatures well above the glass transition temperature of PLLA block (T-g(PLLA)), the PLLA chains started to crystallize, leading to reorientation of lamellae. Such reorientation behavior exhibited dependence on the correlation between the crystallization temperature (T-c), the glass transition temperature of PS (T-g(PS)), the peak melting point of PLLA crystals (T-m(PLLA)), and the end melting point of PLLA crystals (T-m,end(PLLA)). When annealed at (T-c =) 80 degrees C (T-c < T-g(PS) < T-ODT, order-disorder transition temperature), 123 degrees C (T-g(PS) < T-c < T-m(PLLA) < T-ODT). 165 degrees C (T-g(PS) < T-m(PLLA) < T-c < T-m,end(PLLA) < T-ODT), the parallel lamellae became perpendicular to the substrate surface, exclusively starting at the edge of surface relief patterns. Meanwhile, the corresponding lamellar spacing was significantly enhanced.

Crystalline morphology of poly(L-lactic acid) thin films

Crystalline morphologies of spin-coated poly(L-lactic acid) (PLLA) thin films under different conditions are investigated mainly with atomic force microscopy (AFM) technique. When PLLA concentration in chloroform is varied from 0.01 to 1% gradually, disordered structure, rod-shape and larger spheres aggregates are observed in thin films subsequently. Under different annealing temperature, such as at 78, 102, 122 degrees C, respectively, we can find most rod-like crystalline aggregates. Interestingly, we observed that nucleation sites locate at the edge of the holes at the original crystalline stage. Then, these holes developed to form chrysanthemum-like and rods subsequently with annealing time meanwhile the size and the shape of crystalline aggregate are changed. In addition. effect of substrate and solvent on morphology is also discussed. On the other hand, the possible mechanism of crystalline morphology evolution is proposed.

Monte Carlo simulation on symmetric ABA/AB copolymer blends in confined thin films

The effects of blend composition on morphology, order-disorder transition (ODT), and chain conformation of symmetric ABA/AB copolymer blends confined between two neutral hard walls have been investigated by lattice Monte Carlo simulation. Only lamellar structure is observed in all the simulation morphologies under thermodynamic equilibrium state, which is supported by theoretical prediction. When the composition of AB diblock copolymer (phi) increases, both lamellar spacing and the corresponding ODT temperature increase, which can be attributed to the variation of conformation distribution of the diblock and the triblock copolymer chains. In addition, both diblock and triblock copolymer, chains with bridge conformation extend dramatically in the direction parallel to the surface when the system is in ordered state. Finally, the copolymer chain conformation depends strongly on both the blend composition and the incompatibility parameter chi N.

Highly oriented tunable wrinkling in polymer bilayer films confined with a soft mold induced by water vapor

The authors report the formation of highly oriented wrinkling on the surface of the bilayer [polystyrene (PS)/poly(vinyl pyrrolidone) (PVP)] confined by a polydimethylsiloxane (PDMS) mold in a water vapor environment. When PVP is subjected to water vapor, the polymer loses its mechanical rigidity and changes to a viscous state, which leads to a dramatic change in Young's modulus. This change generates the amount of strain in the bilayer to induce the wrinkling. With a shape-controlled mold, they can get the ordered wrinkles perfectly perpendicular or leaned 45 S to the channel orientation of the mold because the orientation of the resultant force changes with the process of water diffusion which drives the surface to form the wrinkling. Additionally, they can get much smaller wrinkles than the stripe spacing of PDMS mold about one order. The wrinkle period changes with the power index of about 0.5 for various values of the multiplication product of the film thicknesses of the two layers, namely, lambda similar to (h(PS)h(PVP))(1/2).

Competition of lamellar orientation in thin films of a symmetric poly(styrene)-b-poly(L-lactide)diblock copolymer in melt state

We have studied the lamellar orientation in thin films of a model diblock copolymer, symmetric poly(styrene)-b-poly(L-lactide) (PS-PLLA), in the melt state on supported silicon wafer surface. In this system, while the PLLA block prefers to wet the polymer/substrate interface, the polymer/air as well as polymer/polymer interface is neutral for both blocks due to the similar surface energies of PS and PLLA in melt state. Our results demonstrate that the interplay of the interfaces during phase separation results in a series of structures before approaching the equilibrium state. Lamellar orientation of thin films with different initial film thicknesses at different annealing stages has been investigated using atomic force microscopy (AFM), transmission electronic microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). It is found that in the early stage (annealing time t < 10 min), the polymer/substrate interface dominates the structure evolution, leading to a parallel lamellar structure with holes or islands formed depending on the initial film thickness. Later on, the neutral air interface becomes important and leads to a transition of lamellar orientation from parallel to perpendicular. It is interesting to see that for films with thickness h > 2L, where L is the bulk lamellar period, the lamellar orientation transition can occur independently in different parallel lamellar domains due to the neutrality of polymer/polymer interface.