Effects of preparation conditions on the morphology and gas permeation properties of polyethylene (PE) and ethylene vinyl acetate (EVA) films

In this study, the effect of film preparation conditions on the gas permeation properties of polyethylene (PE) and ethylene vinyl acetate (EVA) films (containing 18 and 28 wt% vinyl acetate) was investigated. Film blowing and phase inversion methods were applied in the production of PE and EVA films, respectively. The permeation of pure oxygen and carbon dioxide gases was measured at room temperature. The results indicated that with the increase of PE film thickness, permeability and solubility of O₂ and CO₂ in these films decreased; but the diffusivities of gases through PE films increased. In addition, in the case of EVA copolymers, by increasing the content of vinyl acetate, the permeability of CO₂ increased. The rate of increase in CO₂ permeability was different for samples having different preparation conditions. For example, the samples prepared using chloroform as the solvent instead of THF, showed lower CO₂ permeability. Also, the morphological studying of film structure indicated that the higher CO₂ permeability for the samples made from THF solvent is due to the existing of higher porosity in the under layer polymer area. Also scanning electron microscopy (SEM) micrographs showed that with the usage of phase inversion method, there will be a thin dense layer near to the glass substrate.     

Solvent penetration and photoresist dissolution: A fluorescence quenching and interferometry study

A novel method, based upon fluorescence quenching measurements, is described for the study of the mechanistic details of solvent penetration into thin polymer films. Here poly(methyl methacrylate) (PMMA) labelled with phenanthrene (Phe) groups was coated as a film (0.8 μm thick) onto quartz disks. Diffusion of solvent (1 : 1 2-butanone/2-propanol) into the film was followed by a decrease in Phe fluorescence, while film dissolution was monitored simultaneously by laser interferometry. In the case of PMMA (M_w = 411,000, films annealed at 160°C) both processes occur at approximately the same rate and exhibit non-Fickian (relaxation-controlled) diffusion behavior. Correlating the results of these two experiments shows that, once the steady state is reached, the dissolution rate is controlled by the advance of the solvent front into the PMMA film. The “transition layer,” an important dissolution parameter, increases its thickness from 50 to 90 nm during the plasticization stage of solvent penetration and maintains its thickness until the solvent front reaches the quartz substrate.     

Influence of solvent and molecular weight on thickness and surface topography of spin-coated polymer films

The influence of polymer molecular weight, molecular weight distribution, and polymer-solvent interactions on the thickness and topography of spin-coated polymer films was examined. For films prepared from dilute solutions, highly volatile solvents or fair or “poor” solvents for the polymer adversely affect film surfaces causing nonuniformities (waves) to appear. However, if the concentration of these solutions is increased to approximately the concentration at which entanglements are formed, nearly uniform films are produced even if the solvent employed is highly volatile, such as dichloromethane. When toluene is employed as the solvent, which has a relatively low volatility and therefore forms nearly flat film surfaces, films prepared from dilute solution were found to have thicknesses, h, proportional to η Ω^?0.49 for polystyrene and η Ω^?0.49 for poly(methylmethacrylate) where η_o is the zero-shear rate solution viscosity and Ω is the rotational speed at which the films were prepared. These results suggest that the exponents associated with η_o and Ω may be nearly independent of the type of polymer used as long as flat films are produced. Finally, the molecular weight parameter most important in controlling final film thickness for films made from dilute solutions is M_v, the viscosity-average molecular weight.     

Synthesis, characterization, and properties of chain terminated polyhedral oligomeric silsesquioxane-functionalized perfluorocyclobutyl aryl ether copolymers

A new class of perfluorocyclobutyl (PFCB) polymers covalently functionalized with polyhedral oligomeric silsesquioxane (POSS) is presented. Three discreetly functionalized POSS monomers possessing thermally reactive trifluorovinyl aryl ether (TFVE) were prepared in good yields. The POSS TFVE monomers were prepared by initial corner-capping of cyclopentyl (-C₅H₉), iso-butyl (-CH₂CH(CH₃)₂), or trifluoropropyl (-CH₂CH₂CF₃) functionalized POSS trisilanols with acetoxyethyltrichlorosilane followed by sequential acid-catalyzed deprotection and coupling with 4-(trifluorovinyloxy)benzoic acid. TFVE-functionalized POSS monomers were thermally polymerized with 4,4′-bis(4-trifluorovinyloxy)biphenyl or 2,2-bis(4-trifluorovinyloxybiphenyl)-1,1,1,3,3,3-hexafluoropropane monomers via a condensate-free, [2 + 2] step-growth polymerization. The polymerization afforded solution processable PFCB polymers with POSS macromer installed on the polymer chain ends. POSS monomers and their corresponding copolymers were characterized by ¹H, ¹³C, ¹⁹F, and ²⁹Si NMR, GPC, ATR-FTIR, and elemental combustion analysis. GPC trace analysis showed agreeable number-average molecular weight for various weight percent of cyclopentyl or iso-butyl and trifluoropropyl chain terminated POSS PFCB copolymers. DSC analysis showed the introduction of increasing POSS weight percent in the endcapped PFCB copolymers lowers the glass transition temperatures as high as 31 °C. On the other hand, the trifluoropropyl POSS endcapped PFCB polymer glass transition temperature was unaffected when copolymerized with the more fluorinated 2,2-bis(4-trifluorovinyloxybiphenyl)-1,1,1,3,3,3-hexafluoropropane monomer. TGA analysis of POSS PFCB copolymers showed step-wise decomposition of copolymers resulting from the initial degradation of the POSS cages at 297-355 °C in nitrogen and air which was confirmed by pyrolysis coupled with GC-MS. This initial weight loss was proportional to the weight percent of POSS incorporated into the polymer. The balance of decomposition was observed at 450-563 °C in nitrogen and air which is higher than the PFCB homopolymers in most cases. Polymer surface characterization was performed on spin cast transparent, flexible films. These composite films exhibited good POSS dispersion within the matrix PFCB polymer as was shown by TEM analysis.     

Geometry and nature of the interfacial layer in polyimide coatings

A new approach to the quantitative evaluation of the thickness h_i and the volume fraction V_i of the interfacial layer in polyimide coatings has been developed using the model of a one-sided polymer coating as a three-phase system (a substrate, an interfacial layer and a polymer matrix) and the method of differential scanning calorimetry. The new approach is characterized by the fact that a “pure” polymer matrix is modeled with the help of free films obtained on mercury. The formulas for the calculation of the thickness and volume fraction of the interfacial layer have been proposed. The value h_i has been determined in polymer coatings of different thicknesses on aluminium foil. This parameter has been shown to be independent of the film thickness if the latter is not larger than the length of the interfacial layer. An assumption has been made about the “mechanical” origin of thick (> 1–5 μm) interfacial layers, and their relaxation character has been revealed.     

Improved thin film stability of differently formulated,printed, and crosslinked polymer layers against successive solvent printing

Interface control remains a top challenge of solution-processed organic light emitting diodes (OLED) stacks since the device performance heavily relies on it. Film stability of an inkjet deposited and crosslinked layer against subsequent exposure to a suitable inkjet printed solvent has been investigated. Impact of processing solvent (solvent used to prepare the polymer layer) on solution-cast thin film properties has already been shown for polymer films. To our knowledge, this study is the first one analyzing thin films stability against solvent exposure using technology relevant materials processed via inkjet printing (IJP). The outcome of this research showed that the stability of the crosslinked films is affected by the solvent used for ink formulation. These findings are of great interest for multilayered semiconductors devices, such as OLEDs, field-effect transistors and dye-sensitized solar cells. Differential scanning calorimetry (DSC) was used to quantify the efficiency of the polymer crosslinking reaction in pure powder and in thin films, as processed from different solvents. Crosslinking efficiency measured by DSC correlated well with the deformation induced by the solvent and observed on layer surfaces. The interaction in solution between polymer and solvent has also been evaluated to explain its impact on thin film stability against successive solvent printing. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48895.     

Moisture absorption into ultrathin hydrophilic polymer films on different substrate surfaces

Moisture absorption into ultrathin poly(vinyl pyrrolidone) (PVP) films with varying thickness was examined using X-ray reflectivity (XR) and quartz crystal microbalance (QCM) measurements. Two different surfaces were used for the substrate: a hydrophilic silicon oxide (SiO_x) and a hydrophobic hexamethyldisilazane (HMDS) treated silicon oxide surface. The total equilibrium moisture absorption (solubility) was insensitive to the surface treatment in the thickest films (≈150 nm). However, strong reductions in the equilibrium uptake with decreasing PVP film thickness were observed on the HMDS surfaces, while the SiO_x surface exhibited thickness independent equilibrium absorption. The decreased absorption with decreasing film thickness is attributed a depletion layer of water near the polymer/HMDS interface, arising from hydrophobic interactions between the surface and water. The diffusivity of water decreased when the film thickness was less than 60 nm, independent of the surface treatment. Changes in the properties of ultrathin polymer films occur even in plasticized films containing nearly 50% water.     

Preparation of superhydrophobic silica‐based films by using polyethylene glycol and tetraethoxysilane

Preparation of superhydrophobic silica‐based films via sol‐gel process by adding polyethylene glycol (PEG4000) in the silica sol precursor solution has been developed. The casting films were prepared by casting the above solution on the glass and adding poor solvent on it or not. Surface roughness of the films was obtained by removing polymer from the films at high temperature. Then, the hydrophobic group on the surfaces was obtained by reaction with hexamethyldisilazane (HMDS). Characteristic properties of the as‐prepared surface of the films were analyzed by contact angle measurement, scanning electron microscopy (SEM), atomic force microscope (AFM), Fourier transform infrared (FT‐IR) spectrophotometer, and X‐ray photoelectron spectrometer (XPS). The results showed that the contact angles of the films were varied with the PEG weight fraction of the films, the solvent for the PEG solution, the reaction temperature and time, and adding poor solvent (n‐hexane) or not. However, the surface roughness has been controlled by adjusting the experimental parameters during the early period. The contact angle of the film that prepared by spraying the poor solvent (n‐hexane) onto each coating layer for four times after casting process was greater than 150°. It was difficult to obtain superhydrophobic surface without adding n‐hexane onto any coating layer in this system. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Alignment layer relaxation—a technique for assessing thermal transitions in polymer films

We introduce a method for assessing the glass transition temperature (T_g) of thin polymer films. The technique may be applied to any polymer film that can effect liquid crystal alignment, and is demonstrated here for a commercial polyamide-imide. The method leverages the ability of the polymer film to align nematic liquid crystals on its surface, when that surface has been prepared by mechanical brushing. Relaxation of the alignment layer, brought about by thermal cycling through T_g, is seen to affect liquid crystal alignment, and thus serve as a T_g indicator. The technique reveals a three-order-of-magnitude change in the measured property. The method allows the assessment of that portion of the film responsible for aligning liquid crystals, and provides an indication of the efficacy of alignment. Our results imply that the relaxation of the surface in Probimide 32 occurs over a range of temperatures, and relaxation is not complete until the film is heated to a temperature above the glass transition of the bulk polymer.     

Preparation and properties of poly[styrene‐co‐(butyl acrylate)‐co‐(acrylic acid)]/silica nanocomposite latex prepared using an acidic silica sol

BACKGROUND: Polyacrylate/silica nanocomposite latexes have been fabricated using blending methods with silica nanopowder, in situ polymerization with surface‐functionalized silica nanoparticles or sol–gel processes with silica precursors. But these approaches have the disadvantages of limited silica load, poor emulsion stability or poor film‐forming ability. RESULTS: In this work, poly[styrene‐co‐(butyl acrylate)‐co‐(acrylic acid)] [P(St‐BA‐AA)]/silica nanocomposite latexes and their dried films were prepared by adding an acidic silica sol to the emulsion polymerization stage. Morphological and rheological characterization shows that the silica nanoparticles are not encapsulated within polymer latex particles, but interact partially with polymer latex particles via hydrogen bonds between the silanol groups and the ? COOH groups at the surface of the polymer particles. The dried nanocomposite films have a better UV‐blocking ability than the pure polymer film, and retain their transparency even with a silica content up to 9.1 wt%. More interestingly, the hardness of the nanocomposite films increases markedly with increasing silica content, and the toughness of the films is not reduced at silica contents up to 33.3 wt%. An unexpected improvement of the solvent resistance of the nanocomposite films is also observed. CONCLUSION: Highly stable P(St‐BA‐AA)/silica nanocomposite latexes can be prepared with a wide range of silica content using an acidic silica sol. The dried nanocomposite films of these latexes exhibit simultaneous improvement of hardness and toughness even at high silica load, and enhanced solvent resistance, presumably resulting from hydrogen bond interactions between polymer chains and silica particles as well as silica aggregate/particle networks. Copyright © 2009 Society of Chemical Industry     

Metalizable Polymer Thin Films in Supercritical Carbon Dioxide

We report an environmentally “green” method to improve adhesion at a polymer/metal interface by using supercritical carbon dioxide (scCO₂). Spun-cast polystyrene (PS) and poly(methyl methacrylate) (PMMA) thin films on cleaned Si wafers were used for this study. Film thicknesses of both polymer films were prepared in the range of 100 Å to 1600 Å. We exposed the films to scCO₂ in the pressure-temperature (P–T) range corresponding to the density-fluctuation ridge, where the excess swelling of both polymer films occurred, and then froze the swollen structures by quick evaporation of CO₂. A chromium (Cr) layer with film thickness of 300–400 Å was deposited onto the exposed film by using an E-beam evaporator. X-ray reflectivity (XR) measurements showed that the interfacial width between the Cr and exposed polymer layers increased by a factor of about two compared with that without exposure to scCO₂. In addition, the large interfacial broadening was found to occur irrespective of the thickness of both polymer films. After the XR measurements, the dewetting structures of the PS/Cr films induced by additional annealing were characterized by using atomic force microscopy, showing improved surface morphology in the exposed films. Contact angle measurements showed that a decrease in interfacial tension with exposure to scCO₂ accompanied the increase in interfacial width.     

Electrodeposition of titanium(IV) oxide film from sacrificial titanium anode in I2-added acetone bath

A TiO₂ film was fabricated by a simple electrochemical method using a sacrificial titanium anode as a cationic source in an I₂-dissolved acetone bath, where the solvent contains iodide ions as a supporting electrolyte but no Ti salt as an electrolyte. At the initial stage of electrolysis, anodic oxidation of Ti anode occurred under the presence of water as an impurity to acetone. Subsequently, TiO²⁺ was produced as a result of the dissolution of oxide films under the influence of iodide ions, and was then electrodeposited on the cathode surface. The morphologies of as-deposited films were found to be dependent on the film thickness, which in turn is determined by the voltage applied during the electrolysis. Moreover, the obtained films show photocatalytic activity for decomposition of gaseous acetaldehyde without annealing. In this paper, the electrodeposition mechanism is discussed in detail.     

Temperature- and thickness-dependent elastic moduli of polymer thin films

The mechanical properties of polymer ultrathin films are usually different from those of their counterparts in bulk. Understanding the effect of thickness on the mechanical properties of these films is crucial for their applications. However, it is a great challenge to measure their elastic modulus experimentally with in situ heating. In this study, a thermodynamic model for temperature- (T) and thickness (h)-dependent elastic moduli of polymer thin films E _f(T,h) is developed with verification by the reported experimental data on polystyrene (PS) thin films. For the PS thin films on a passivated substrate, E _f(T,h) decreases with the decreasing film thickness, when h is less than 60 nm at ambient temperature. However, the onset thickness (h*), at which thickness E _f(T,h) deviates from the bulk value, can be modulated by T. h* becomes larger at higher T because of the depression of the quenching depth, which determines the thickness of the surface layer δ.     

Dynamic mechanical property and interlaminar shear strength of the carbon fabric reinforced polyetherimide composite based on the polyetherimide resin films

In this study, the laminates reinforced with the concentrated nitric acid or acetone treated carbon fabrics were prepared based on polyetherimide films with different thickness including 30 μm and 50 μm, respectively. 4 Harness Satin (4HS) and 5 Harness Satin (5HS) carbon fabrics were used as the reinforcements of the composite laminates. Three impact factors, including the polyetherimide film thickness, fabric treatment method and fabric type, were considered in this study. Interlaminar shear strength (ILSS) measurement shown that the thicker polyetherimide film (50 μm), 4HS carbon fabric and the nitric acid treatment of the fabric could be used to increase the ILSS value because of the improvement of the interfacial property for the laminate. The 50 μm thickness polyetherimide films used in the laminates improved the storage modulus, and decreased the glass transition temperatures (T _gs) by DMA or DSC. It was because that the better interfacial property and the stronger mobility of the polymer chain under the greater residual internal stress in the laminate was obtained with the increase of the polyetherimide film thickness. The nitric acid treatment of the fabric increased the T _gs measured by DMA and DSC, and decreased the tan δ peak values of the laminates because of the stronger interfacial adhesion between the fiber and the resin and the decreased mobility of the polymer chain. In addition, the effects of above three impact factors on the ILSS, storage modulus, loss modulus, tan δ and the T _g of the laminate were discussed in detail by ILSS, DMA and DSC measurement, respectively. POLYM. COMPOS., 38:663–672, 2017. © 2015 Society of Plastics Engineers     

On the thickness and spatial distribution of a fluoropolymer film deposited by solution dipping

Poly-1H,1H-pentadecafuorooctyl methacrylate is a barrier compound used to prevent silicone oil from creeping to relay contacts. It is essentially a methyl methacrylate polymer with a fluorocarbon side chain substituted for one of the methyl hydrogens. It is applied by dipping the part into a solution, with Freon TF as the solvent and the fluorocarbon polymer as the solute. This work considers the spatial distribution of the resulting film of barrier compound when it is deposited in this manner. The specific variables considered are concentration and withdrawal velocity. The samples were withdrawn from the solution with velocity perpendicular to the surface, and we show that the macrosopic uniformity and thickness of the film is dependent on this velocity. There exists a critical velocity (dependent on concentration) above which the film is nonuniform and below which the film is macroscopically uniform. Below the critical velocity, the thickness varies with velocity with approximately a v^2/3 dependence. The critical velocity is about 13 mm/sec for a concentration of 0.2%. For macroscopically uniform films, a microscopic nonunitormity exists with a coverage of about 1/4 for an average film thickness of 90 Å.     

A facile approach to the fabrication of ultrathin polymer films and application to optical lenses

A facile approach to the fabrication of ultrathin polymer films on a flat or curved substrate is presented. Polymers with unsaturated pendant groups were spin-coated on a photoinitiator tethered surface, which was then photoirradiated and washed with a solvent. The obtained films were uniform, smooth (R_a < 0.2 nm) and exhibited robustness toward solvents. The thickness of the films was determined by the molecular weight of the coated polymer and was not dependent on the initial spin-coated thickness. A mechanism for the formation of the ultrathin film and application to optical lenses is presented.     

Synthesis and properties of polyurethane‐urea‐based liquid bandage materials

To obtain ideal liquid bandage polymer materials, a series of polyurethane‐urea dispersions were synthesized from 4,4′‐diisocyanato dicyclohexylmethane (H₁₂MDI) and ethylene diamine with different molar ratio of polyol blend [polyethylene glycol (PEG, M_n = 2000 g/mol)/hydroxy terminated poly(dimethylsiloxane) (PDMS, M_n = ～ 550 g/mol)] and acetone/ethanol as a solvent. The effect of PDMS content in PEG/PDMS on the viscosity, mechanical properties, water contact angle/surface energy, insolubility in water (%), water absorption (%), equilibrium water content (%), and water vapor transmission rate (g m^?2 day^?1) of polyurethane‐urea films was investigated. As PDMS content increased, the water contact angle, insolubility in water, and tensile strength/elastic recovery of film sample increased; however, the surface energy, water absorption (%), equilibrium water content (%), and water vapor transmission rate (g m^?2 day^?1) of film sample decreased. By a wound‐healing evaluation using a full‐thickness rat model experiment, it was found that a wound covered with a typical polyurethane‐urea liquid bandage film (PD2 sample) was filled with new epithelium without any significant adverse reactions. These results suggest that the polyurethane‐urea‐based liquid bandages (samples: PD2 and PD3) prepared in this study may have high potential as new wound dressing materials, which provide and maintain the adequate wet environment required to prevent scab formation and dehydration of the wound bed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Coagulation of polymer–Cu2+ complexes in polymer films and its application for producing semiconducting CuI surface layers

In poly(vinyl alcohol) and polyacrylamide films containing the corresponding polymer–Cu²⁺ complexes, the reason why the films may gain surface electrical semiconductivity as high as 10^?3 Ω^?1 when treated with acetone solution of iodine was investigated. Optical and scanning electron microscope observations indicated that the coagulated polymer–Cu²⁺ complexes favor the appearance of the high conductivity and that the state of coagulation depends on the anions of the copper salts used as well as two parameters, F₁ ≡ [Cu²⁺]/[MU] and F₂ ≡ [OH^?]/[Cu²⁺], where [MU] is the molar concentration of monomeric units of the polymer and [OH^?] is that of hydroxide ions added. The effectiveness of the anions in causing coagulation decreases in the order of SO₄^2? > Cl^? > NO₃^? ≈ Br^?. The whitish substance that appears on the film surface after the iodine treatment gives x-ray Debye–Scherrer rings characteristic of γ-CuI. The γ-CuI surface layer adheres to the film rather firmly, at least in polyacrylamide, and is responsible for the conductivity. By controlling the state of coagulation of the complexes and hence the formation of the γ-CuI surface layer, we have produced films with anisotropic surface electrical semiconductivity, i.e., σ_∥ ≈ 10^?4 Ω^?1 and σ_∥/σ_⊥ = 1 ? 10³. Optical and ESR spectra are also obtained to understand the mechanism of γ-CuI formation and to clarify the optical properties of the films.     

Measuring and modelling the transition layer during the dissolution of glassy polymer films

The technique of laser interferometry is now used routinely by the microelectronics industry for the measurement of the dissolution rates of thin polymer films. In addition to the rate of dissolution, laser interferometry can also provide quantitative information on the thickness of the transition layer between the dissolving glassy polymer and the liquid solvent. This paper describes how observed patterns of reflected light intensity may be analyzed to calculate the thickness of the transition layer for polymers that dissolve with little or no swelling. The technique requires knowledge of the shape of the concentration profile in the transition layer. However, by assuming various simple model profiles one may obtain a reasonable estimate. Experimental measurements of poly(methyl methacrylate) (PMMA) films dissolving in methylethyl ketone indicate transition layers of thicknesses 0 to 0.1 μm for PMMA of molecular weights M_w = 37,000 to 1,400,000.