Tuning hydrophobicity of a fluorinated terpolymer in differently assembled thin films

In the current report, casting from good solvent (acetone) and casting from mixed solvent and nonsolvent were employed for preparing thin films of terpolymer of T etrafluoroethylene (TFE), H exafluoropropylene (HFP), and V inylidene fluoride (VDF) (THV), on silicon wafers. These films revealed various morphologies and wetting behaviors depending on the solution concentration, temperature, and thin film preparation method. The THV thin films prepared by casting from good solvent showed smooth morphology with holes. The thin film prepared from a 3 wt % THV/acetone solution by casting from good solvent at 15 °C demonstrated spheres in addition to the smooth morphology, while the thin film prepared from a 5 wt % THV/acetone solution at 15 °C by casting from good solvent had a mesh‐like structure with some linked spheres. Casting the thin films from mixed solvent and nonsolvent resulted in various morphologies such as different sphere sizes embedded in a dense film layer, and hexagonal close packed structures. The thin films prepared by casting from good solvent showed a slightly hydrophobic character, with a measured water contact angle of approximately 99°, while the nonsolvent cast films had a water contact angle as high as 145°. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 643–657     

Reversible Morphology Control in Block Copolymer Films via Solvent Vapor Processing: An In Situ GISAXS study

The real time changes occurring within films of cylinder-forming poly(α-methylstyrene-block-4-hydroxystyrene) (PαMS-b-PHOST) were monitored as they were swollen in tetrahydrofuran (THF) and acetone solvent vapors. In situ information was obtained by combining grazing incidence small angle X-ray scattering (GISAXS) with film thickness monitoring of the solvent vapor swollen films. We show that for self assembly to occur, the polymer thin film must surpass a swollen thickness ratio of 212% of its original thickness when swollen in THF vapors and a ratio of 268% for acetone vapor annealing. As the polymer becomes plasticized by solvent vapor uptake, the polymer chains must become sufficiently mobile to self assemble, or reorganize, at room temperature. Using vapors of a solvent selective to one of the blocks, in our case PHOST-selective acetone, an order-order transition occured driven by the shift in volume fraction. The BCC spherical phase assumed in the highly swollen state can be quenched by rapid drying. Upon treatment with vapor of a non-selective solvent, THF, the film maintained the cylindrical morphology suggested by its dry-state volume fraction. In situ studies indicate that self-assembly occurs spontaneously upon attaining the threshold swelling ratios.     

The influence of selective solvents on the transition behavior of poly(styrene-b-monomethoxydiethylenglycol-acrylate-b-styrene) thick films

Thick poly(styrene-b-monomethoxydiethylenglycol-acrylate-b-styrene) [P(S-b-MDEGA-b-S)] films (thickness 5 μm) are prepared from different solvents on flexible substrates by solution casting and investigated with small-angle X-ray scattering. As the solvents are either PS- or PMDEGA-selective, micelles with different core-shell micellar structures are formed. In PMDEGA-selective solvents, the PS block is the core and PMDEGA is the shell, whereas in PS-selective solvents, the order is reversed. After exposing the films to liquid D₂O, the micellar structure inside the films prepared from PMDEGA-selective solvents remains unchanged and only the PMDEGA (shell part) swells. On the contrary, in the films prepared from PS-selective solvents, the micelles revert the core and the shell. This reversal causes more entanglements of the PMDEGA chains between the micelles. Moreover, the thermal collapse transition of the PMDEGA block in liquid D₂O is significantly broadened. Irrespective of the solvent used for film preparation, the swollen PMDEGA shell does not show a prominent shrinkage when passing the phase transition, and the transition process occurs via compaction. The collapsed micelles have a tendency to densely pack above the transition temperature.     

Solvent vapor annealing of block copolymer thin films: removal of processing history

The ordering processes of PS-b-P2VP block copolymer thin films with different processing histories were studied during solvent vapor annealing by in situ grazing incidence small-angle X-ray scattering (GISAXS). We compared cylinder-forming PS-b-P2VP thin films with 34 kg/mol molecular weight that were prepared in three different ways: spin coating, spin coating and subsequent solvent vapor annealing where the solvent vapor was removed instantaneously, and spin coating and subsequent solvent vapor annealing where the solvent vapor was removed slowly. Block copolymer thin films retained the morphology resulting from the different “processing histories” at smaller swelling ratios. This processing history was erased when the samples reached a higher swelling ratio (~1.4). After the solvent was slowly removed from the swollen film, the surface morphology was characterized by ex situ AFM. All samples showed the same morphology after solvent annealing regardless of the initial morphology, indicating the morphology of solvent annealed samples is determined by the polymer concentration in the swollen film and the solvent vapor removal rate, but not the processing history.     

An in situ GISAXS study of selective solvent vapor annealing in thin block copolymer films: Symmetry breaking of in-plane sphere order upon deswelling

Thin films of asymmetric poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) block copolymers are studied by means of in situ grazing-incidence small-angle X-ray scattering (GISAXS) during solvent vapor annealing in tetrahydrofuran, a solvent selective for the PS majority block of the copolymer. Upon swelling, PS-b-P4VP block copolymers form hexagonal arrays of spherical P4VP microdomains in a PS matrix in films 7–9 layers thick. Deswelling the films induces a transition from hexagonal to face-centered orthorhombic (fco) symmetry, which is stable only at ∼7 layers of spherical microdomains. Dry films show co-existing hexagonal and orthorhombic symmetries when the solvent is removed slowly, whereas instantaneous solvent removal suppresses the fco structure, resulting in films with only hexagonal structure. The in-plane order of microdomains is significantly deteriorated in dry films independent of the solvent removal rate.Spherical block copolymer microdomains are known to undergo a transition from hexagonal to orthorhombic packing in isothermally annealed thin films when the number of sphere layers is increased from 4 to 5. In this paper, in situ GISAXS experiments reveal that a similar transition occurs during solvent vapor annealing in a selective solvent. Interestingly, the transition from hexagonal to orthorhombic packing of spheres occurs as solvent is removed from a thin block copolymer film. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 331–338     

Synthesis and characterization of (hydroxypropyl)cellulose/TiO2 nanocomposite films

A new method of synthesis of TiO₂ nanoparticles as well as preparation of the organic–inorganic hybrid nanocomposite films of (hydroxypropyl)cellulose (HPC)/TiO₂ is presented. At the first stage, the oxotitanium hydrogel phase was obtained by the mineralization of (tetra‐isopropyl)orthotitanate (TIPT) modified by the methacrylic acid (MAA) in 15 wt% solution of H₂O₂ at room temperature and subsequent annealing at the temperature of 85°C. The crystallization of the nanoparticles of TiO₂ was conducted at the oxotitanium hydrogel phase at temperatures around 120°C in the closed vessel. Nanocomposite hybrid films were prepared by the casting method from a solution of HPC and TiO₂ nanoparticles in the water. The films of nanocomposite with 10 µm thickness are transparent to visible light and have a lower glass transition temperature compared with HPC in the bulk. This shift of the glass transition is interpreted in terms of packing density of HPC in the interface of HPC nanocomposite with TiO₂. The X‐ray diffraction pattern of the nanocomposite film suggests a lower amount of mesomorphic phase of HPC in the composite compared with HPC in the bulk. Copyright © 2007 John Wiley & Sons, Ltd.     

Effects of humidity,imidization history,and thickness on water sorption behavior of poly(p-phenylene biphenyltetracarboximide) films

Poly(p-phenylene biphenyltetracarboximide) films with various thicknesses were prepared from the poly(amic acid) precursor by thermal imidization at 230–400°C for 1–10 h under a nitrogen atmosphere. The water sorption in the films was measured at 25°C over 22–100% relative humidity using a Cahn microbalance as a function of film thickness and thermal imidization history. The water diffusion in all the films followed nearly Fickian process despite the morphological heterogeneity due to the ordered and less ordered phases. The diffusion coefficient and water uptake varied in 0.85 × 10^?10 ? 7.50 × 10^?10 cm²/s and 0.12–2.4 wt %, respectively, depending upon humidity, film thickness, and imidization history. Both diffusion coefficient and water uptake increased with increasing humidity, but decreased as imidization temperature and time increased. With increasing film thickness, the diffusion coefficient increased whereas the water uptake decreased. The water sorption behavior was interpreted with the consideration of morphological variations, such as polymer chain order, in-plane orientation, and intermolecular packing order due to the film thickness and imidization history. © 1995 John Wiley & Sons, Inc.     

Electron beam irradiation of poly(vinyl methyl ether) films. 2. Temperature-dependent swelling behavior

Temperature-sensitive hydrogel films were synthesized by electron beam irradiation of poly(vinyl methyl ether) (PVME) on silicon (Si/SiO(2)) substrates and gold (Au) coated glass slides. The temperature-dependent swelling behavior of the films in aqueous solution was characterized by in situ spectroscopic ellipsometry and a combination of surface plasmon resonance (SPR) and optical waveguide spectroscopy (OWS). The results of both techniques are compared. The suitability of both techniques for the characterization of the swelling behavior of thin hydrogel films is demonstrated. The volume swelling degree in the swollen state decreases with increasing radiation dose D. This is explained by the fact that the number of formed polymeric radicals, and hence cross-linking density, increases with D. Above the phase-transition temperature, the swelling degrees were independent of D, slightly above 1. The swelling/deswelling process was fully reversible and is mainly directed perpendicular to the substrate surface. The phase-transition temperature was determined to be T(cr) approximately 33 degrees C. However, T(cr) slightly decreases with increasing D and increasing film thickness d.     

Evolution of water vapor from indium-tin-oxide transparent conducting films fabricated by dip coating process

Tin-doped indium oxide In₂O₃ (indium-tin-oxide) transparent conducting films were fabricated on silicon substrates by a dip coating process. The thermal analysis of the ITO films was executed by temperature-programmed desorption (TPD) or thermal desorption spectroscopy (TDS) in high vacuum. Gas evolution from the ITO film mainly consisted of water vapor. The total amount of evolved water vapor increased on increasing the film thickness from approx. 25 to 250 nm and decreased by increasing the preparation temperature from 365 to 600°C and by annealing at the same temperature for extra 10 h. The evolution occurred via two steps; the peak temperatures for 250 nm thick films were approx. 100-120 and 205-215°C. The 25 nm thick films evolved water vapor at much higher temperatures; a shoulder at approx. 150-165°C and a peak at approx. 242°C were observed. The evolution temperatures increased by increasing the preparation and the annealing temperatures except in case of the second peak of the 25 nm thick films. The evolution of water vapor at high temperature was tentatively attributed to thermal decomposition of indium hydroxide, In(OH)₃, formed on the surface of the nm-sized ITO particles. This revised version was published online in August 2006 with corrections to the Cover Date.     

Extraction and Purification of Purple Membrane for Photochromic Thin Film Development: Application in Photoelectrochemical Investigation

Purple membrane (PM) has been extracted and purified from archaebacteria for thin film development. The purified purple membrane is isolated in 1?% polyvinyl alcohol solution for making thin film within gelatin and organically modified silicate matrices. For thin film within gelatin matrix, homogenized purple membrane suspension is mixed with 8?% gelatin and poured into a specially designed block with desired thickness of spacer having hydrophobicity followed by gelatinization of the same over home-made thermostatic control unit at 38?°C. The gelatinized matrix is then allowed to dry under controlled conditions of humidity and temperature. The films of varying thicknesses ranging between 40, 50, and 60??? are used for photo-electrochemical measurements. The results on photo-electrochemistry of non-oriented purple membrane film provides valuable information on the generation of forward (light on) and backward (light off) photocurrent as a function of: (a) applied potential and (b) film thickness. An increase in applied negative potential increases the amplitude of photocurrent whereas decrease in film thickness facilitates the reversibility of photocurrent response.     

Effects of deposition temperature and annealing temperature on the morphology and electrochemical capacitance of Ni(OH)2 thin films

In this paper, we report 3D nickel (II) hydroxide thin films with porous nanostructures prepared on Ni foam by direct current electrodeposition from aqueous solution of Ni(NO₃)₂ through basic chemicals. The effect of deposition temperature on Ni(OH)₂ thin film morphology is examined by field emission scanning electron microscopy, which is found to have significant influence on capacitance performance of Ni(OH)₂ thin films. Moreover, the effect of annealing temperature on electrochemical capacitance and long-time stability of Ni(OH)₂ thin films is investigated. An optimum-specific capacitance value of 2,447?farads?g^?1 is obtained for Ni(OH)₂ thin film deposited at 20?°C and annealed at 100?°C.     

Surface modification by deposition of IPA plasma and gellan gum/chitosan hybrid hydrogel onto thermoplastic polyurethane for controlled release of N‐acetylcysteine

A thin film system composed of gellan gum and chitosan was fabricated through a combination of polyelectrolyte blend and hybrid hydrogel gelation for controlled release of drug. In this study, precursor isopropyl alcohol (IPA) was used to plasma deposit on the surface of thermoplastic polyurethane (TPU) to form a hydrophilic film. The features of the thin film were evaluated using water contact angle (WCA) measurement, scanning electron microscopy (SEM), Fourier transform infra‐red (FTIR), UV/Vis spectroscopy, and studies of controlled release of drugs. The hybrid hydrogel, pH‐sensitive, was tested at pH values of 1.2 and 7.4 of buffer solution and at a temperature of 37°C to observe its swelling ratio and drug delivery properties with N‐acetylcysteine as a drug material for controlled release. Furthermore, at pH 7.4, the hybrid hydrogel has an outstanding release ratio of up to about 90% absorption amounts of N‐acetylcysteine after 8 hr. The mechanism of drug release from thin film devices (n = 0.684) is anomalous (non‐Fickian) transport, the value of n lies between 0.43 and 0.85.     

Moisture absorption and absorption kinetics in polyelectrolyte films: influence of film thickness

Specular X-ray reflectivity (XR) and quartz crystal microbalance (QCM) measurements were used to determine the absorption of water into thin poly(4-ammonium styrenesulfonic acid) films from saturated vapor at 25 degrees C. The effect of film thickness on the absorption kinetics and overall absorption was investigated in the range of thickness from (3 to 200) nm. The equilibrium swelling of all the films irrespective of film thickness was (0.57+/-0.03) volume fraction. Although the equilibrium absorption is independent ofthickness, the absorption rate substantially decreases for film thickness < 100 nm. For the thinnest film (3 nm), there is a 5 orders of magnitude decrease in the diffusion coefficient for water.     

High‐rate crystallization of polycarbonate in spincast thin film

Surface morphology of bisphenol‐A polycarbonate (BAPC) thin films, with thickness ranging from 30 to 1000 nm on silicon substrates was studied by atomic force microscopy. The films were prepared by spincasting from 1,2‐dichloroethane solutions of 0.25–5.0 wt % BAPC. Even though longer annealing than 250 h was necessary for complete crystallization for bulk BAPC, high crystallinity was observed for 30 nm thick film after annealing at 200 °C for 48 h in vacuum. Positron annihilation lifetime spectroscopy measurements showed that the free volume hole size in 30 nm thick film was larger than that of bulk at 200 °C. Comparison of the BAPC concentration in the precursor solution with the overlap concentration suggests that the high crystallinity of the 30 nm BAPC film is due to less entangled chains caused by rapid removal of the solvent from the dilute solution. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Low-temperature preparation of nanocrystalline anatase films through a sol-gel route

Nanocrystalline anatase (TiO₂) films were prepared at very low temperature through a sol-gel route using titanium isopropoxide and hydrogen peroxide in ethanol. Crystallization occurred after film deposition at 35°C in an atmosphere saturated with water vapor. Both thin and thick films of nanocrystalline anatase were prepared. Observed particle size in crystallized films is approximately 20–40 nm as measured with AFM. No residual organic material was apparent through FTIR after crystallization occurred. Dynamic light scattering studies performed on this system indicate that particle size measured in solution is strongly dependent on the amount of agitation samples received prior to measurement.     

Preparation of Hot Water-Resistant Silica Thin Films from Polysilazane Solution at Room Temperature

Perhydropolysilazane (PHPS) films were deposited on single-crystal Si substrates by spin-coating using a xylene solution of PHPS, and then suspended over 1 mol L^?1 ammonia water at room temperature. The PHPS-to-silica conversion occurring on the exposure to the ammonia water vapor was studied by infrared absorption spectroscopy. Si--H and N--H infrared absorption peaks decreased and Si--O--Si bands increased, showing PHPS-to-silica conversion; the conversion was almost completed in 6 h. The exposed films were soaked in 80°C water for 24 h, and the reduction in thickness on soaking was evaluated. The PHPS-derived films suspended over the ammonia water for 6 h exhibited only 2% reduction in thickness on soaking in 80°C water. Alkoxide-derived silica gel films dried in the ambient atmosphere or suspended over the ammonia water, on the other hand, exhibited significant reduction in thickness on soaking in 80°C water.     

Surface morphology of poly(cyano-p-xylylene) thin films

The surface morphology of poly(cyano-p-xylylene) thin films of different thicknesses (25–1500 nm or more than 5 μm) that were synthesized by vapor-deposition polymerization on the substrate surface in the temperature range from −22 to +35°C has been studied by atomic force microscopy. The surface topography is quantified through analysis of the height-height correlation function. The surface of all films is characterized by a similar granular morphology with a transverse size of granules of 50–500 nm. The surface morphology changes with the polymerization temperature (the substrate temperature) and the film thickness. The effect of film annealing on its surface morphology is considered. It has been established that annealing at 200°C leads to a change in the surface morphology of the films. Original Russian Text ? A.I. Buzin, D.S. Bartolome, K.A. Mailyan, A.V. Pebalk, S.N. Chvalun, 2006, published in Vysokomolekulyamye Soedineniya, Ser. A, 2006, Vol. 48, No. 9, pp. 1640–1646. This work was supported by the Russian Foundation for Basic Research (project nos. 03-03-32665 and 03-03-32634) and the Russian Science Support Foundation.     

Structure and dielectric properties of HfO<Subscript>2</Subscript> films prepared by a sol–gel route

Mono- and multilayer HfO₂ sol–gel thin films have been deposited on silicon wafers by dip-coating technique using a solution based on hafnium ethoxide as precursor. The densification/crystallization process was achieved by classical annealing between 400 and 600 °C for 0.5 h (after drying at 100 °C). Systematic TEM studies were performed to observe the evolution of the thin film structure depending on the annealing temperature. The overall density of the films was determined from RBS spectrometry correlated with cross section (XTEM) thickness measurements. After annealing at 450 °C the films are amorphous with a nanoporous structure showing also some incipient crystallization. After annealing at 550 °C the films are totally crystallized. The HfO₂ grains grow in colonies having the same crystalline orientation with respect to the film plane, including faceted nanopores. During annealing a nanometric SiO₂ layer is formed at the interface with the silicon substrate; the thickness of this layer increases with the annealing temperature. Capacitive measurements allowed determining the value of the dielectric constant as 25 for four layer films, i.e. very close to the value for the bulk material.     

Preparation and properties of ionic‐liquid‐containing poly(ethylene glycol)‐based networked polymer films having lithium salt structures

Ionic‐liquid‐containing polymer films were prepared by swelling poly(ethylene glycol)‐based networked polymers having lithium salt structures with an ionic liquid, 1‐ethyl‐3‐methylimidazolium bis(fluorosulfonyl)imide (EMImFSI), or with an EMImFSI solution of lithium bis(trifluoromethanesulfonyl) imide (LiTFSI). Their fundamental physical properties were investigated. The networked polymer films having lithium salt structures were prepared by curing a mixture of poly(ethylene glycol) diglycidyl ether and lithium 3‐glycidyloxypropanesulfonate or lithium 3‐(glycidyloxypropanesulfonyl)(trifluoromethanesulfonyl)imide with poly(ethylene glycol) bis(3‐aminopropyl) terminated. The obtained ionic‐liquid‐containing films were flexible and self‐standing. They showed high ionic conductivity at room temperature, 1.16–2.09 S/m for samples without LiTFSI and 0.29–0.43 S/m for those with 10 wt % LiTFSI. Their thermal decomposition temperature was above 220 °C, and melting temperature of the ionic liquid incorporated in the film was around ?16 °C. They exhibited high safety due to good nonflammability of the ionic liquid. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and phase‐separation behavior of α,ω‐difunctionalized diblock copolymers

A series of diblock copolymers of n‐pentyl methacrylate and methyl methacrylate (PPMA/PMMA BCP) with one or two terminal functional groups was prepared by sequential anionic polymerization of PMA and MMA using an allyl‐functionalized initiator and/or and end‐capping with allyl bromide. Allyl functional groups were successfully converted into OH groups by hydroboration. The morphology in bulk was examined by temperature‐dependent small‐angle X‐ray measurements (T‐SAXS) and transmission electron microscopy (TEM) showing that functional groups induced a weak change in d‐spacings L₀ as well as in the thermal expansion behavior. T‐SAXS proved that the lamellar morphologies were stable over multiple heating/cooling cycles without order‐disorder transition (ODT) until 300 °C. While non‐functionalized BCP formed parallel lamellae morphologies, additional OH‐termination at the PMMA block forced in very thin films (ratio between film thickness and lamellar d‐spacing below 1) the generation of perpendicular lamellae morphology through the whole film thickness, as shown by Grazing‐incidence small‐angle X‐ray scattering experiments (GISAXS) measurements. Functionalized BCP were successfully used in thin films as templates for silica nanoparticles in an in‐situ sol–gel process. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011