Bending-beam measurement of solvent diffusions in polyimides: Theoretical and experimental

A general formula correlating the bending curvature variation ratio of a layered structure caused by solvent-induced swelling in its polymer overcoat with diffusion time under case II diffusion has been presented. In the event of case II diffusion, the diffusion front velocity, v, can be calculated by using this formula and measured by a bending-beam apparatus. At room temperature, the diffusion of n-methyl-pyrrolidone (NMP) solvent in the film of pyromellitic phenylene diamine (PMDA-PDA) is case II. While in PMDA-B (-benzidine) and benzophenone tetracarboxylic dianhydride (BPDA-PDA), no diffusion progress can be observed. But, the diffusion in 6F-dianhydride- (6FDA-PDA) is case I with D = 0.85 × 10^?9 cm²/s. It becomes anomalous when mixing with 25% PMDA-B, but becomes case II diffusion with more PMDA-B. The preabsorbed moisture in the films does not affect the v value. In PMDA-PDA, v = 7.3 × 10^?8 cm/s. In the 25/75 and 50/50 6FDA-PDA/PMDA-B blends, v = 6.3 and 11.3 × 10^?8 cm/s.     

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.     

Nanomechanical study of polymer‐polymer thin film interface under applied service conditions

Single layer and multilayer polymer thin film coating on polymer substrate are gaining significant importance in different industries. The quantitative and qualitative estimation of interface response for thin film coating under different service conditions is significantly important from the perspective of modeling and designing novel materials. However, to characterize an interface between the soft polymer layer and soft polymer substrate is challenging because of the confinement effect, surface roughness, the viscoelastic nature of the polymers involved, and most importantly, the comparable mechanical properties of soft polymeric film and polymer substrate. Nanoindentation technique was applied in this work to find out the mechanical response of thin film PMMA (100–200 nm) and Epoxy interfaces of different interfacial strengths. Interfaces of different strengths were obtained by exposing the film‐substrate system to different service conditions. It has been observed from this study that pile‐up plays a major role in finding out the mechanical response of the interfaces of different strengths. The hardness was observed to increase as the interfacial strength reduces. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43532.     

Failure modes in organic coatings studied by scanning acoustic microscopy

Scanning acoustic microscopy (SAM) has been found to be well suited to study physically and chemically induced changes and defects in polymer coatings exposed to corrosive environments. In this work, SAM was used to investigate sub-surface migration and blister formation in polymer coatings of different layer structure after exposure to a corrosive solution. Two model systems consisting of base coat and clear coat on steel substrates where studied. The time evolution of sub-surface migration fronts and blister initiation and their growth were investigated by analysing SAM images after different exposure times. Depending on the layer structure, it was possible to differentiate between transport of the electrolyte solution (i) through the coating and (ii) along the coating/substrate interface. Samples without clear coat typically showed randomly distributed blisters at the coating/substrate interface, irrespective of the location of initial defects. The random distribution of blisters is related to diffusion of the electrolyte solution through the coating layer followed by “nucleation” at weak spots of the substrate, at the interface between polymer and substrate or within the polymer. In contrast, samples with a clear coat acting as a diffusion barrier showed a sub-surface migration front of 2–4 μm height, propagating along the coating/substrate interface, starting at initial defects. The linear propagation of this front cannot be explained by Fickian diffusion and is discussed in terms of an accelerated diffusion or crack growth kinetics. Since blistering started only at regions, where the migration front has already passed, the presence of electrolyte solution or water at the coating/substrate interface was found to be a prerequisite for the nucleation of blisters.     

Pellet‐buffered film seed to grow single grain bulk YBCO

Epitaxial thin film seeds, exhibit a higher peritectic temperature than the bulk, have been recognized as a possible way to obtain large‐sized single‐grain REBCO bulks. Recently, use of a pellet as a buffer layer inserted between the film‐seed and the main pellet has been reported. This approach can prevent Mg diffusion from the MgO substrate to the film seed, and enable the thin film to tolerate a higher maximum temperature in the TSMG (Top Seed Melt Growth) method. However, we found that the liquid phase decomposed from YBa₂Cu₃O_7?x(YBCO) contacted the MgO substrate, due to surface tension, and caused undesirable grain nucleation. To resolve this problem, this study used a mini‐pellet, smaller than the seed, as a buffer layer. This new technique can avoid the liquid phase contacting the MgO substrate, thereby allowing the YBCO single‐grain bulk to be grown more easily. Moreover, the thin film seed can be re‐used by removing the buffer layer after the crystal growing process.     

Diffusion of moisture in poly(p-phenylene terephthalamide) film: Analysis by the adsorption-controlled diffusion equation

Diffusion of moisture in poly(p-phenylene terephthalamide) films was observed using a gravimetric method at various vapor pressures at 25°C. The equilibrium moisture regain was 4.9% (g/g) and 4.2% (g/g) at 65% relative humidity for the 16-μm and 50-μm thick film, respectively. These values are slightly larger than regular Kevlar or Kevlar 49 that have the same chemical structure of poly(p-phenylene terephthalamide) (PPTA). The sorption and desorption curves were satisfactorily analyzed by the adsorption-controlled diffusion equation assuming reversible bimolecular kinetics. These results strongly indicate that the interaction between the water molecules and amide groups of polymer plays an important role in the diffusion process and has much effect on the shape of sorption/desorption curves. The diffusion coefficients for the films were in the order from 10^−-11 to 10^−-10 cm²/s, which were also larger than those for Kevlar fibers of 10^−-12 cm²/s. The higher moisture diffusivity in the film reflects sparser molecular packing and existence of interstitial microvoids due to the lower molecular orientation in the noncrystalline region in the PPTA film than in the fiber (Kevlar).     

Non-fickian diffusion with reaction in glassy polymers with swelling induced by the penetrant—effects of consecutive and parallel reactions

A mathematical model is presented for non-Fickian diffusion of a penetrant A into a granular glassy polymer containing a reactive group B, resulting in the desired product P. Further, both a consecutive reaction between A and P (producing X) and a parallel reaction between A and C (producing Y) are incorporated, with C initially present in the particle. The swelling of the polymer, induced by the penetrant, is described by power-law kinetics for the velocity of the swelling front. Kinetics are considered to be first order in each of the two reactants. Concentration profiles in the particle and selectivity to desired product are calculated as function of the swelling behavior of the polymer grain. In case of a consecutive reaction the local concentration of P reaches a maximum value independent of the swelling rate. However, the position of the maximal concentration of P moves towards the center of the grain with a rate depending on the kinetics of swelling. For Case II diffusion this velocity equals the velocity of the advancing front between glassy and rubbery polymer. The selectivity of the desired reaction decreases with decreasing swelling rate. A low swelling rate also results in an inhomogeneous product distribution within the granule. A criterion is derived predicting under what conditions the consecutive reaction can be neglected and a pure product is obtained. The analysis further reveals that both a more homogeneous product and a higher selectivity toward a desired product can be obtained by realizing preswelling of the polymer with an inert swelling agent. For Case II diffusion the concentration profiles of the side product of the parallel reaction, Y, are flat in the rubbery part of the polymer. This is caused by the relatively low swelling rate allowing Y to redistribute in the swollen polymer. If additional C is continuously supplied from the gas phase, then the selectivity decreases continuously with increasing conversion of B.     

Assembly of 8YSZ nanoparticles into gas-tight 1-2 μm thick 8YSZ electrolyte layers using wet coating methods

The application of a thin film electrolyte layer with a thickness in the micrometer range could greatly improve current solid oxide fuel cells (SOFCs) in terms of operating temperature and power output. Since the achievable minimal layer thickness with conventional powder coating methods is limited to ∼5 μm, a variety of thin film methods have been studied, but results on regular large-scale anode substrates are still lacking in the literature. In this paper, a wet coating process is presented for fabricating gas-tight 1-2 μm thick 8YSZ electrolyte layers on a regular NiO/8YSZ substrate, with a rough surface, a high porosity and a large pore size. These layers were deposited in a similar way as conventional suspension based layers, but the essential difference includes the use of coating liquids (nano-dispersion, sol) with a considerably smaller particle size (85 nm, 60 nm, 35 nm, 6 nm). Successful deposition of such layers was accomplished by means of an innovative coating process, which involves the preparation of a hybrid polyvinyl alcohol/8YSZ membrane by dip-coating or spin-coating and subsequently burning out the polymer part at 500 °C. Results from He leak tests confirmed that the sintered layers posses a very low number of defects and with values in the range 10⁻⁴-10⁻⁶ (hPa dm³)/(s cm²) the gas-tightness of the thin film layers is satisfactory for fuel cell operation. Moreover, preliminary results have also indicated a potential reduction of the sintering temperature from 1400 °C to the range 1200-1300 °C, using the presented coating process.     

Surface fluorination of transparent polymer film

Transparent polymer film was fluorinated by contacting with fluorine gas. The fluorinated layer depth was determined from the visual spectrum. The relation between fluorinated depth d and reaction time t was represented by d = k·t^½. This result indicates that fluorine diffusion plays a predominant role in forming the diffusion profile. The apparent activation energy of fluorine gas diffusion into polystyrene (PS) and polycarbonate (PC) was 2.8 kcal/mole and 6.6 kcal/mole, respectively. The refractive index distribution from surface to center, which corresponds to the fluorine content in the layer, was determined by interference microscopy. PS and PC showed nearly stepwise change of refractive index. On the other hand, poly(methyl methacrylate) showed a gradual change. These results are compatible with fluorine analysis data and IR spectra of the fluorinated polymers. On the basis of these results, antireflecting layers on plastic lens or plate, plastic optical fiber, or fiber sheet were formed.     

Mineralization of hydroxyapatite on a polymer substrate in a solution supersaturated by polyelectrolyte

In this article, a new method to construct composites of hydroxyapatite (HAP) and polymer material is introduced. A previously developed method for mineralization of CaCO₃ on a polymer substrate was applied to HAP. A solution that contained Ca²⁺, PO₄^3–, and OH‐ ions was supersaturated with polyacrylic acid (PAA) that, at the same time, formed a polymer complex with the substrate, a polyvinyl alcohol (PVA) film, at the substrate surface. In this thin surface layer, nucleation of HAP took place. Subsequently, the disklike domains of HAP that were generated spread until they covered the PVA film surface. By regulating the pH of the supersaturated solution at around 7.4, the domain size decreased and the quantity of deposited material increased. Approximately 20 mg of HAP coating was obtained on a PVA film of 1 cm radius when the film was soaked in single 200 mL batch of the supersaturated solution for 21 days. The junction between HAP layer and PVA substrate film was found to be very firm. When a crosslinked PVA/PAA was used as the substrate, the film swelled in the supersaturated solution to form a hydrogel. Then mineralization took place within the gel, and a transparent monolithic composite of HAP and the polymer network was obtained. In 13 days, the weight increase was 29 mg, which corresponded to a 71 wt % HAP mineralization ratio of the composite. By changing crosslinking degree and HAP mineralization ratio, the flexibility of composite will be controlled in a wide range. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1465–1470, 2006     

The study of diffusion of solvents from the coating films during the curing process by bulk acoustic wave admittance analysis

The diffusion of solvents from a coating layer and their evaporation at the surface of the coating film during the curing process of the coating are investigated by bulk acoustic wave (BAW) admittance analysis and can be expressed as change in the relative diffusion rate (J). The porosity and permeability of the coating film are related to the curing degree (η). The changes in J and the values of J₃ (the relative diffusion rate at the surface dry time, t_s), Δt_p (the time difference between the surface dry time t_s and the turning point time t_p when the diffusion behaviour changes), and η can provide much useful information on selecting solvents and optimizing coating ingredients in the preparation of coatings. The effects of the coating film thickness, solvent content of the coating liquid, and the volatility of the solvent on the diffusion of solvent from the film are also discussed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 563–571, 1997     

Surface acoustic waves in diamond-like carbon films on LiNbO3

Diamond-like carbon (DLC) films have been reliably deposited on YZ LiNbO_3, and surface acoustic wave (SAW) velocity change has been observed. These relatively thin films increase the SAW velocity sufficiently, and they can be used for SAW devices. The cut-off behavior was observed at approximately 538 MHz in a 2-μm-thick DLC film on the LiNbO₃ substrate.     

Thermal stability and performance of optimized ZrCx diffusion barriers in ceramic coating systems for ATF applications

Surface-modified Zr alloy claddings with advanced ceramic coatings are promising materials for accident-tolerant fuel (ATF) systems to meet stringent safety regulations concerning light water reactors. The applications of ceramic coatings are, however, limited as a result of inferior thermal stability when used in conjunction with Zircaloy-4 (Zry-4) substrates. Herein, the thermal stability of sub-stoichiometric zirconium carbide barrier layers as a function of composition was studied. Integrated ceramic coatings comprising ZrC_0.55 diffusion barriers and a Cr₂AlC top layer were synthesized via a magnetron sputtering method. After rapid thermal annealing, the ZrC_0.55 barrier layer having a thickness of 0.5 μm effectively prevented the inter-diffusion between Cr₂AlC and the Zry-4 substrate, thereby ensuring retention of the structural integrity of the integrated ceramic coating system for ATF applications.     

Interdiffusion between silica thin films and soda-lime glass substrate during annealing at high temperature

We study the diffusive interaction between soda-lime glass substrates and sputtered aluminum-doped silica thin films at 650°C, the temperature of commercial soda-lime glass shaping or tempering. A first rapid migration of alkali ions from substrate to thin film has been described in a companion paper (J Am Ceram Soc. 2018;101:1516). Using the same samples as (J Am Ceram Soc. 2018;101:1516), we focus here on later interactions, when the layer is consumed by the substrate resulting from diffusive interactions. Using Secondary Ion Mass Spectroscopy profilometry, we show that the interdiffusion rate increases with the aluminum doping content of the layer. We show that the alkali uptake of silica layers accelerates diffusive exchanges with the substrate, consistently with a decrease of viscosity of the layer. Diffusion profiles of silicon are well reproduced when solving the diffusion equation for a diffusivity having an exponential dependence with silicon concentration. The diffusivity of aluminum is shown to be 10 times slower than the diffusion of silicon. Specific exchanges of the two network formers with network modifiers are deduced from the composition-space trajectories, providing evidence for multicomponent diffusive couplings between species.     

Formation and characterization of perfluorocyclobutyl polymer thin films

Perfluorocyclobutyl (PFCB) polymers are a new class of materials that show promise as selective layer materials in the development of composite membranes for gas separations, such as carbon dioxide/methane (α_{pure gas} = 38.6) and oxygen/nitrogen (α_{pure gas} = 4.8) separations. In many of the flat sheet applications, a thin film of the selective layer that is free of major defects must be coated onto a support membrane. A focus of this study was to elucidate the impacts of solvents, polymer concentration, and dip‐coating withdrawal speed on PFCB thin film thickness and uniformity. An extension was proposed to the Landau–Levich model to estimate the polymer film thickness. The results show that the extended model fits the thickness‐withdrawal speed data well above about 55 mm/min, but, at lower withdrawal speeds, the data deviated from the model. This deviation could be explained by the phenomenon of polymer surface excess. Static surface excesses of polymer solutions were estimated by applying the Gibbs adsorption equation using measured surface tension data. Prepared films were characterized by ellipsometry. Refractive index was found to increase with decreasing film thickness below about 50 nm, indicating densification of ultrathin films prepared from PFCB solutions below the overlap concentration. Atomic force microscopy was used to characterize surface morphologies. Films prepared from tetrahydrofuran and chloroform yielded uniform nanolayers. However, films prepared using acetone as solvent yielded a partial dewetting pattern, which could be explained by a surface depletion layer of pure solvent between the bulk PFCB/acetone solution and the substrate. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Bending-beam study of water sorption by thin poly(methyl methacrylate) films

A bending-beam technique has been employed to study the effects of film thickness (7–55 μm) and rate of cooling during film preparation (～ 6°C/h to a dry ice quench) on sorption characteristics of water by poly(methyl methacrylate) films coated on thin fused quartz beams (? 84 μm thick). In each experiment, the curvature of a polymer coated beam exposed to liquid water was monitored as a function of time by a low power laser pointer. With the use of a transport model which considers the sorption process as the linear superposition of contributions from Fickian diffusion and a first-order polymer molecular relaxation process, the beam curvature data were analyzed to determine the governing transport kinetics and associated transport parameters such as water diffusion coefficient and relaxation rate constant. From curvature analysis for thin films (7–13 μm in thickness), it was found that water diffusion proceeds at early times in a Fickian-like manner with a diffusion constant of 2–4 × 10^?9 cm²/s. At later times, significant relaxation contributions lead to non-Fickian diffusion behavior, an effect that is more pronounced as the film thickness or sample cooling rate decreases. In addition, sorption of water was found to reduce the film stress (initially tensile at ? 10⁸ dyn/cm²) at a rate that increases with sample cooling rate. The high initial film stress not present in free-standing films may account for the relatively higher diffusion coefficient (～ 2 × 10^?8 cm²/s) found here for very thick (55 μm) PMMA coatings. Because the bending-beam technique uses coated samples, it is especially well suited for studying penetrant transport into polymer coatings.     

Visualizing spatial and temporal heterogeneity of single molecule rotational diffusion in a glassy polymer by defocused wide-field imaging

Defocused wide-field fluorescence microscopy was used to follow the 3D molecular rotational diffusion of a fluorescent probe molecule in a polymer thin film. The technique allows for visualizing the molecular reorientation both in-plane and out-of-plane. The local environmental change driven by heterogeneous dynamics of the polymer can be probed on a scale of 1 μm as demonstrated by parallel imaging of several molecules. A multi-component rotational diffusion decay is observed which might reflect both different relaxation regimes of the polymer as well as rapid changes of the local environment.     

Photoactive mussels inspired polymer coatings: Preparation and antibacterial activity

In this article we report on the facile preparation of photoactive antibacterial mussel inspired polymer coatings deposited on a stainless steel (SS) substrate from water based precursors. The coating is prepared by the sequential deposition of aqueous based solutions of an anchoring layer based on bio-inspired glue, a cationic polymer bearing pendent catechols, a nanogel decorated by ortho-quinones and a photosensitizer of the aminoacridine type. This latter is grafted to the coating by reaction of its amino group with the o-quinone of the deposited nanogel. The deposition of all layers is followed in-line by Quartz crystal microbalance coupled with dissipation (QCM-D) and AFM shows that the thin polymer film repeated the roughness of the SS substrate. The prepared coatings show good mechanical properties applying nanoindentation techniques. The established antibacterial activity of the prepared photoactive polymer coatings on SS against Gram-negative E. coli strain demonstrate their potential as a power tool for medical applications.     

Characteristics of nFOG,an aerosol-based wet thin film coating technique

An atmospheric pressure aerosol-based wet thin film coating technique called the nFOG is characterized and applied in polymer film coatings. In the nFOG, a fog of droplets is formed by two air-assist atomizers oriented toward each other inside a deposition chamber. The droplets settle gravitationally and deposit on a substrate, forming a wet film. In this study, the continuous deposition mode of the nFOG is explored. We determined the size distribution of water droplets inside the chamber in a wide side range of 0.1–100 µm and on the substrate using aerosol measurement instruments and optical microscopy, respectively. The droplet size distribution was found to be bimodal with droplets of approximately 30–50 µm contributing the most to the mass of the formed wet film. The complementary measurement methods allow us to estimate the role of different droplet deposition mechanisms. The obtained results suggest that the deposition velocity of the droplets is lower than the calculated terminal settling velocity, likely due to the flow fields inside the chamber. Furthermore, the mass flux of the droplets onto the substrate is determined to be in the order of 1 g/m³s, corresponding to a wet film growth rate of 1 µm/s. Finally, the nFOG technique is demonstrated by preparing polymer films with thicknesses in the range of approximately 0.1–20 µm.