Highly transparent memory states in polymer dispersed liquid crystal films

Abstract

Electro-optical properties of polymer dispersed liquid crystal (PDLC) films which have reversed morphology are investigated. Highly transparent memory states, for which transmittances exceed more than 80 per cent, are observed in these PDLC films. The saturation voltage V ₉₀ can be decreased by a PTF (a phase transition with a field) operation and becomes 10 times lower than that without PTF operation. A contrast ratio of more than 600 is obtained in the memory state of a thick PDLC film.     

Stabilization of Film Morphology in Polymer‐Fullerene Heterojunction Solar Cells

Abstract

The fixation of film morphology is essential for the long‐term stability of heterojunction polymer photovoltaic (PV) cells. An epoxy‐functionalized fullerene C₆₀ derivative was synthesized for this purpose. This material can be polymerized at acidic conditions and was found to stabilize the phase‐separated morphologies within blended polythiophene–fullerene heterojunction films. The phase stability of the films was characterized by UV‐VIS spectroscopy and optical microscope. Crosslinkable polythiophene derivatives were also prepared but these materials were much less effective in stabilizing film morphology when mixed into PCBM (C61‐butyric acid methyl ester). Heterojunction polymer PV cells were prepared from these materials and their performance was compared with cells made from conventional materials.     

Controlling morphological and electro-optical properties via the phase separation in polymer/liquid-crystal composite materials

ABSTRACT

The polymer/liquid-crystal composite materials have been extensively studied for their potential applications. Various optical devices based on this composite material have been proposed and realised. The device performance is highly dependent on the phase separation of this composite material. Here, we investigate the photopolymerisation-induced phase separation in this composite material. Depending on the mass ratios between the polymer and the liquid crystal, the phase separation can be well controlled and subsequently affect the morphological and electro-optical properties. At a fixed ratio, we can realise either phase-separated composite films or conventional polymer-dispersed liquid crystal films with completely different optical properties. By carefully controlling the exposure conditions, the morphologies and electro-optical properties have been studied and optimised in details. With in-depth studies and optimisation, the photopolymerisation-induced phase separation technique could be utilised to realise many different optical functions based on the polymer/liquid-crystal composite materials.     

Fabrication of Gold Nano‐Structures with Azopolymer Templates

Fabrication of gold nano‐patterns has been demonstrated employing surface relief structures created on films of an azobenzene‐functionalized polymer as templates. The surface relief templates were photoinscribed on the azopolymer films in one‐step with two laser beams. Thin layers of gold were over‐coated on the polymer templates by thermal evaporation. Gold lines of a few hundred nanometer width were successfully fabricated by pyrolyzing the azobenzene polymer. Sub‐micron gold dots were also created. The resulting gold structures exhibited the same periodicity as the polymer templates.     

Microdomain morphology of lamella‐forming diblock copolymer confined in a thin film

We report the self‐consistent field theory (SCFT) of the morphology of lamella‐forming diblock copolymer thin films confined in two horizontal symmetrical/asymmetrical surfaces. The morphological dependences of thin films on the polymer‐surface interactions and confinement, such as film thickness and confinement spatial structure, have been systematically investigated. Mechanisms of the morphological transitions can be understood mainly through the polymer‐surface interactions and confinement entropy, in which the plat confinement surface provides a surface‐induced effect. The confinement is expressed in the form of the ratio D/L₀, here D is film thickness, and L₀ is the period of bulk lamellar‐structure. Much richer morphologies and multiple surface‐induced morphological transitions for the lamella‐forming diblock copolymer thin films are observed, which have not been reported before. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1–10, 2009     

Atomic layer deposition of metal-oxide thin films on cellulose fibers

Abstract

Atomic layer deposition (ALD) is a vapor-phase technique capable of producing inorganic thin films with precise control over the thickness of the film. The ALD method offers high precision in the design of advanced 3D nanostructures. In this article, silica and alumina thin films have been grown over fibers of cellulose by the ALD process. The morphology and the chemical composition of the fabricated thin films are characterized, as well as their thermal durability through elevated temperatures. Moreover, XPS is used to confirm the phases of the alumina nanofilms and to further understand the deposition process on the cellulose microfibers.     

THE FORMATION AND STABILITY OF MICROSCOPIC EMULSION FILMS OF AQUEOUS SOLUTIONS OF POLY (ACRYLIC ACID) AND ACRYLIC ACTD-VINYLACETATE COPOLYMERS

ABSTRACT

The effect of polymer volume concentration C, pH and ionic strength (NaCl concentration, CNal) of solution, polymer molecular mass, acetate groups' content in a polymer chain, and ethanol concentration on the stability of microscopic emulsion films (MEF) stabilized with the adsorption layers of poly(acrylic acid) (PAA) and acrylic acid-vinylacetate copolymers (PAA-VA) has been studied.

The kinetics of MEF thinning under the conditions when two heptane drops in a polymer solution are brought into contact and pressed with a permanent force has been studied.

The free energy ? F of interaction in the film has been evaluated on the basis of measuring the film thickness Hf by photometry and determining the film profile in the Plateau region.     

MOLECULAR TRANSPORT OF ORGANIC LIQUIDS THROUGH POLYMER FILMS

Abstract

The molecular transport of small molecules through polymer films has been the subject of active research over almost three decades [1–8]. The main thrust in this area is either to accumulate a large body of experimental data to assess the stability of polymer films for extreme serviceability or to develop new theories which describe the phenomenology of transport processes, the latter often being studied in terms of three important parameters: permeation, diffusion, and solubility, in adition to the swelling phenomenon.     

Molecular orientation and liquid crystal alignment properties of new cinnamate-based photocrosslinkable polymers

Isotropic thin films of three original phenyl substituted cinnamate-based polymers, here-after referred to as 'Para', 'Meta' and 'Metamet' have been exposed to linearly polarized UV light and their photoinduced molecular orientations have been studied. The resulting photocrosslinked anisotropic polymer films were characterized using UV, conventional and polarization modulation (PM) FTIR spectroscopies. From UV and PM-IR linear dichroism measurements, at least two simultaneous orientation processes appear to play a key role in these phenyl substituted cinnamate-based systems. On the one hand, isomerization reactions deplete chromophores along the polarization direction (P) of the UV light and induce a preferential orientation of remaining 'trans'-isomers perpendicular to P; on the other hand, cycloaddition reactions lead to the formation of either head to head or head to tail photodimers aligned preferentially along P in the 'Para' and to a lesser extent in the 'Meta' and 'Metamet' systems. These last results are related to the different liquid crystal alignment properties of the films, and the influences of the chemical structure of the chromophores are discussed.     

Swift heavy ion induced modification in dielectric and microhardness properties of polymer composites

Polymer composites with different concentrations of organometallics (ferric oxalate) dispersed PMMA were prepared. PMMA was synthesized by solution polymerization technique. These films were irradiated with 120 MeV Ni¹⁰⁺ ions in the fluence range 10¹¹-5 × 10¹² ions/cm². The radiation induced modifications in dielectric properties, microhardness, structural changes and surface morphology of polymer composite films have been investigated at different concentrations of filler and ion-fluences. It was observed that electrical conductivity and hardness of the films increase with the concentration of the filler and also with the fluence. The dielectric constant (?) obeys the Universal law given by ?αfⁿ⁻¹. The dielectric constant/loss is observed to change significantly due to irradiation. This suggests that ion beam irradiation promotes the metal to polymer bonding and convert polymeric structure into hydrogen depleted carbon network. This makes the composites more conductive and harder. Surface morphology of the films has been studied using atomic force microscopy (AFM) and scanning electron microscopy (SEM). The average surface roughness is observed to increase after irradiation as revealed by AFM studies. The SEM images show the blisters type of phenomenon on the surface due to ion beam irradiation.     

The effects of energetic ion irradiation on metal-to-polymer adhesion

In this study, the simple and effective surface modification of polymers through ion irradiation is described to improve metal-to-polymer adhesion. The surface of polymer films was irradiated with 150 keV Xe⁺ ions at various fluences, and copper (Cu) was then deposited onto the surface-modified polymer films. The surface properties of the modified films were investigated in terms of their wettability, chemical composition, and surface morphology. The metal-to-polymer adhesion strength was estimated using a nano-indenter. As a result, the surface environment of the polymer films was physiochemically changed by ion irradiation, which could have a significant effect on the metal-to-polymer adhesion. The irradiated polymer films exhibited a higher adhesion strength than the control film, and the strength depended on the fluence. The maximum adhesion strength (8.45 mN) of the Cu deposited on the irradiated PEN films was obtained at a fluence of 5×10¹⁴ ions/cm².     

Polymer chain organization and orientation in ultrathin films: A spectroscopic investigation

The effect of confinement on the crystallinity and chain orientation of ultrathin poly(di-n-hexylsilane) films has been investigated using UV absorption, fluorescence and IR spectroscopies. UV absorption measurements in a series of poly(di-n-hexylsilane) films having thicknesses between 50 and 3500 Å have shown that, for thicknesses less than 500 Å, the polymer backbone disorders and extensive crystallization of the films is hindered irrespective of molecular weight or surface hydrophobicity. Fluorescence studies showed that rapid energy transfer occurs from the disordered chain segments to the crystalline ones. The orientation of both the polymer backbone and side chains was probed with IR absorption and grazing incidence reflection measurements. The side chains are extended, although not completely in the all-trans conformation, with their carbon plane mostly perpendicular to the substrate. The backbone lies extended, with the polymer axis parallel to the plane of the film. The hexyl side-chains disorder in films less than 2000 Å thick and this disordering occurs through the introduction of gauche bonds. Our findings suggest the possibility of using thickness to control the chain organization and morphology of a polymer thin film. © 1996 John Wiley & Sons, Inc.     

Columnar nanostructured polymer films containing ionic liquids in supramolecular one-dimensional nanochannels

Ionic liquids have attracted a considerable attention as the next generation electrolytes for energy devices. We have developed new free-standing and nanostructured polymer films in which ionic liquids are confined into one-dimensionally ordered nanochannels. These polymer films have been obtained by photopolymerization of hydrogen-bonded supramolecular columnar liquid-crystalline self-assemblies of an imidazolium-based ionic liquid and a wedge-shaped diol compound containing polymerizable groups. The macroscopically parallel alignment of the columnar structures on a glass substrate has been achieved by the application of mechanical shearing, and subsequently fixed into polymer films by UV irradiation. This ionic liquid-containing polymer film exhibits higher ionic conductivity than that of the previously reported one-dimensional polymer film obtained by in situ photopolymerization of a covalent-type columnar liquid-crystalline imidazolium salt. The noncovalent supramolecular approach to one-dimensionally ion-conductive polymer films has led to improvement on conductive properties. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 366–371     

Investigation of Morphology and Chemical Structure of Nanosized Polytetrafluoroethylene Films Deposited on the Surface of Track-Etched Membranes by Plasma Processing

The morphology and chemical structure of nanosized polytetrafluoroethylene films deposited on the surface of track-etched poly(ethylene terephthalate) membranes by means of radiofrequency magnetron sputtering and electron-beam sputtering of the polymer in a vacuum have been studied using atomic force microscopy and X-ray photoelectron spectroscopy. It has been established that the morphology of films formed with the use of these coating techniques varies considerably. This is due to the size of the deposited polymer particles. The particles formed by the electron-beam sputtering of polytetrafluoroethylene are larger than those produced by magnetron sputtering of the polymer. It has been shown that the chemical composition of the films deposited by electron-beam sputtering in a vacuum is more in line with the composition and structure of the initial polymer than the films obtained by radiofrequency magnetron sputtering.     

Influence of chain length of prepolymers in permanent memory effect of PDLC assessed by solid-state NMR

ABSTRACT

The relationship between linear chain (ethylene oxide units) length of polymerisable monomers with morphology, electro-optical properties and ¹³C nuclear magnetic resonance (NMR) spectroscopy of the corresponding polymer-dispersed liquid crystal (PDLC) films was investigated. The preferred liquid crystal molecule alignment and permanent memory effect of PDLC were greatly influenced by the length of the molecular chain of prepolymers to be incorporated as a polymer matrix. By increasing the number of ethylene oxide in prepolymer chain and maintaining the number of functionalities (polymerisable groups in each monomer molecule), the permanent memory effect of PDLC increased, as proved by solid-state ¹³C NMR spectroscopy.     

RUPTURING OF POLYMER FILMS WITH RUBBING-INDUCED SURFACE DEFECTS

It has been a long-standing question whether dewetting of polymer film from non-wettable substrate surfaceswherein the bicontinuous morphology never forms in the dewetting film is due to spinodal instability or heterogeneousnucleation. In this experiment, we use a simple method to make the distinction through introduction of topographical defectsof the films by rubbing the sample surface with a rayon cloth. Spinodal dewetting is identified for those films that dewet by acharateristic wavevector, q, independent of the density of rubbing-induced defects. Heterogeneous nucleation, on the otherhand, is identified for those with q increasing with increasing density of defects. Our result shows that PS films on oxidecoated silicon with thickness less than ≈ 13 nm are dominated by spinodal dewetting, but the thicker films are dominated bynucleation dewetting. We also confirm that spinodal dewetting does not necessarily lead to a bicontinuous morphology in thedewetting film, contrary to the classic theory of Cahn.     

The influence of preparation method of OC1OC6-PPV films on the photo-oxidation process

Poly(p-phenylene vinylene) (PPV) derivatives are well known for their applications in polymer light emitting diodes (PLEDs). PPV derivatives are highly susceptible to photo-oxidation though, which is mainly caused by the scission of the vinyl double bond on the polymer backbone. In this work, we show that Langmuir-Blodgett (LB) films are less degraded than cast films of a PPV derivative (OC₁OC₆-PPV). Both films had similar thickness (∼50 nm) to allow for a more realistic comparison. Degradation was monitored with UV-vis and FTIR spectroscopies. The results indicated that cast films were completely degraded in ca. 400 min, while LB took longer time, i.e. about four times the values for the cast films. The differences can be attributed to the more compact morphology in the LB than in the cast films. With a compact morphology the diffusion of oxygen in the LB film is hampered and this causes a delay in the degradation process.     

Study of structural and dielectric behaviour on carbon nano tube dispersed {xPVF: (1 − x)CH3COONH4} electrolyte

In the present work, improvement in ion transport property of polyvinyl formal (PVF)-based nanocomposite polymer electrolytes has been studied upon dispersal of multiwall carbon nanotube (MWCNT) filler. Nanocomposite polymer electrolyte (NCPE) films of xPVF: (1 ? x)CH₃COONH₄ (ammonium acetate) were prepared by solution cast technique. The formation of nanocomposite has been ascertained by X-ray diffraction (XRD) pattern, which also shows that doping of salt increases amorphousness through polymer salt complexation. Changes in surface morphology have been observed in optical microscopy and Scanning Electron Microscopic (SEM) images. Variation of dielectric constant, dielectric loss, tangent loss and modulus spectra with the change in frequency and temperature were studied with the aid of impedance spectroscopy.     

Spectroscopic and Discharge Studies on Graphene Oxide Doped PVA/PVP Blend Nanocomposite Polymer Films

Graphene oxide (GO) nanoparticles were synthesized by modified Hummers method. The synthesized GO nanoparticles were incorporated in polyvinyl alcohol/polyvinyl pyrrolidone (PVA/PVP) blend polymers for the preparation of nanocomposite polymer films by solution cast technique. Different characterizations such as XRD, UV–Vis and FTIR were carried-out on to the prepared nanocomposite polymer films. The thermal analysis of the films was studied by DSC. The morphology of PVA/PVP:GO polymer films confirms GO was exfoliated within the PVA/PVP matrix and also reveals the heterogeneous phase of nanocomposite polymer electrolyte systems. From the conductivity studies the highest conductivity of PVA/PVP: GO (0.45: 0.3) was found to be 8.05 × 10^–4 S/cm at room temperature. Solid state battery has been fabricated with the configuration of Mg⁺/(PVA/PVP:GO)/(I₂ + C + electrolyte) and its cell parameters were calculated for a constant load of 100 kΩ.     

Effect of NiO nanofiller concentration on the properties of PEO-NiO-LiClO4 composite polymer electrolyte

Composite polymer electrolyte films comprising polyethylene oxide (PEO) as the polymer host, LiClO₄ as the dopant, and NiO nanoparticle as the inorganic filler was prepared by solution casting technique. NiO inorganic filler was synthesized via sol-gel method. The effect of NiO filler on the ionic conductivity, structure, and morphology of PEO-LiClO₄-based composite polymer electrolyte was investigated by AC impedance spectroscopy, X-ray diffraction, and scanning electron microscopy, respectively. It was observed that the conductivity of the electrolyte increases with NiO concentration. The highest room temperature conductivity of the electrolyte was 7.4?×?10^?4 S cm^?1 at 10 wt.% NiO. The observation on structure shows the highest conductivity appears in amorphous phase. This result has been supported by surface morphology analysis showing that the NiO filler are well distributed in the samples. As a conclusion, the addition of NiO nanofiller improves the conductivity of PEO-LiClO₄ composite polymer electrolyte.