Film Stratification Research Articles

Stratification of polyisocyanate in two-component waterborne polyurethane films

The coatings industry continually seeks advancements in waterborne two-component polyurethane (2 K WBPU) systems, given their potential for environmentally friendly applications and superior film properties. This study explores the mechanistic aspects of film formation in 2 K WBPU coatings formulated with an acrylic polyol and a polyisocyanate (PIC) derived from a trimer of hexamethylene diisocyanate (HDI-trimer). To enhance water dispersibility—a key parameter in industrial applications—the HDI-trimer is modified with a short polyethylene glycol, producing a hydrophilically modified PIC (hmPIC). While prior studies identified hmPIC as an effective reactive plasticizer for the polyol, the common practice of adding unmodified HDI-trimer (uPIC) to hmPIC for moisture sensitivity reduction necessitates a deeper understanding of film properties. Using fluorescence resonance energy transfer (FRET) and confocal fluorescence microscopy, we investigated the effects of blending uPIC with hmPIC on coalescence, phase separation, and film stratification in 2 K WBPU systems. Notably, environmental factors like relative humidity were found to influence film stratification significantly. This finding has critical implications for coating performance, such as durability and water resistance. A novel method was also introduced to monitor water permeation within stratified films, offering a valuable tool for optimizing film properties in real-world applications. This study underscores the importance of strategic component interactions in polymer coatings, suggesting that controlled film stratification can significantly enhance film performance in industrial settings.

Materials Based on Amorphous Al2O3 and Composite W-Al2O3 for Solar Coatings Deposited by High-Rate Sputter Processes

In parabolic trough technology, the development of thermally and structurally stable solar coatings plays a key role in determining the efficiency, durability, and economic feasibility of tube receivers. A cermet-based solar coating is typically constituted by a thin film stratification, where a multilayer graded cermet is placed between an infrared metallic reflector and an antireflection filter. This work reports the realization of materials based on Al2O3 and W characterized by high structural and chemical stability in vacuum at high temperature, obtained through the optimization of high-deposition-rate processes. Al2O3 material, employed as the antireflection layer, was deposited through a reactive magnetron sputtering process at a high deposition rate. Cermet materials based on W-Al2O3 were deposited and employed as absorber layers by implementing reactive magnetron co-sputtering processes. An investigation into the stability of the realized samples was carried out by means of several material characterization methods before and after the annealing process in vacuum (1 × 10−3 Pa) at high temperature (620 °C). The structural properties of the samples were evaluated using Raman spectroscopy and XRD measurements, revealing a negligible presence of oxides that can compromise the structural stability. Spectrophotometric analysis showed little variations between the deposited and annealed samples, clearly indicating the high structural stability.

Self-Stratifying Particulate Coating for Robust Superhydrophobic and Latex-Repellent Surface

A technique for preparing superhydrophobic and natural latex-repellent surface requires at least two fabrication components: surface roughness, and surface layer with low free energy. Here, multiscale surface roughness in micro-/nanoscales with low surface energy can be simultaneously achieved through the deposition of fluoroalkyl-functionalized silica aggregates. However, the mechanical durability of such film remains problematic. Therefore, third component such as polymer binder was incorporated carefully to improve adhesion between film-substrate interface without deteriorating surface roughness and surface energy. In this work, we employed self-stratifying coating technique to induce vertical phase separation between particles and polymer during film drying, such that the silica aggregates densely accumulated on the top surface, while polymer binder concentrated near the film bottom. The governing transports during film stratification process involve diffusion and convection driven by evaporation. Thus, this research focused on the effect of drying temperature and evaporation rate on the anti-wetting performance of the coating. The results showed that the liquid-repellent properties of the surface improve with increasing drying temperature, indicating the convection-dominated transport that induced substantial particle trap at the film surface. With polymer binder added, the coatings still showed decent superhydrophobic and natural latex-repellent properties with maximum contact angles 166.4°±0.6° and 157.5°±0.5°, as well as minimum sliding angles 2.7°±0.3° and 2.9°±0.2° for water and natural latex respectively. Also, AFM result revealed that significant surface roughness of 581 ± 18 nm was still achievable even at high blending mass ratio of polymer binder up to half of the silica weight.

Self-stratified bio-based coatings: Formulation and elucidation of critical parameters governing stratification

Self-stratification is an innovative one-step process used to design multi-functional coatings gathering simultaneously in a one-pot formulation the primer, the intermediate layer and the top coat properties. Many self-stratifying coatings contain oil-based epoxy resins but the literature is scarce in the development of “greener” solutions. In this work, silicone resins and bio-based epoxy resins were dissolved in various solvent blends, applied on a composite substrate and cured under different conditions to obtain stratified coatings. To reach a perfect stratification, the influence of various parameters including (i) the surface tension and the polarity of the resins, (ii) the solvents volatility, (iii) the curing temperature and (iv) the reactivity of the epoxy/amine reaction was studied by a systematic approach. In accordance with the literature, it was demonstrated that a large difference in surface energy and polarity favors resins separation. The volatility of the solvent blend was also shown to be a key factor in the stratification process. However, the predominant parameter, rarely taken into account, is the curing temperature, which impacts the cross-linking reaction of the epoxy resin. The increase in molecular weight (MW) of epoxy resins due to the cross-linking reaction favors the incompatibility between resins by increasing the difference in MW between epoxy and silicone resins. Thus, optimization of process conditions allowed the design of perfectly stratified bio-based epoxy/silicone coatings. The mechanism of film stratification was also elucidated thanks to in-situ analyses.

On the effect of particle surface chemistry in film stratification and morphology regulation.

Combinations of colloids and binders are often used to formulate functional coatings. In these mixtures, competition between particle migration, polymer chain diffusion, evaporation and sedimentation affects their respective spatial location and therefore can govern the surface features. In addition to this, the surface chemistry of the nanoparticles (NPs) and the resulting interparticle interactions can play a significant role in dictating the morphology and the properties of resultant films. Hence it would be possible to tune the surface and bulk topology of the films by controlling these parameters. A combination of various acrylic binders with two types of silica sols, bare (BSiO2) and modified silica (MSiO2), differing in their ability to gel, were formulated and dried under controlled conditions. Factors influencing the mobility and migration of binder and silica particles were evaluated with respect to particle concentration and drying rate. MSiO2 films showed prominent pores with gradual increase in Si% across the cross-section of the films, whereas, BSiO2 films had no pores and showed a uniform Si content across the cross-section of the films. This difference is explained by the variation in gelation between BSiO2 compared to MSiO2, that hindered the NPs migration and affects the infiltration and stratification process. This study paves a path forward to achieve desired surface and bulk porosity from colloidal silica coatings by effective control of chemistry of particles along with process parameters.

Gas flow mechanism and pressure analysis in plates in micro scale gas film

PurposeThe purpose of this paper is to develop the micro-electro-mechanical systems (MEMS) technology has created the conditions for the study of microfluidic technology. Microfluidic technology has become a very large branch in the MEMS field over the past decade. For aerostatic thrust bearing, the micro-fluidic gas flow in a small-scale gas film between two parallel plates is the subject of many studies. Because of the thin gas in the film, velocity slip occurs at the interface, which causes the gas flow pattern to change in the lubricating film. So, it is important to clarify the mechanism and pressure characteristics in thin firm gas flow.Design/methodology/approachFirst, a new assumption and corresponding models for the flow regime were established by theoretical analysis. Second, computational simulations about pressure distribution and velocity were given by a large-scale atomic/molecular massively parallel simulator (LAMMPS). Third, comparison of the results of LAMMPS simulation and direct simulation Monte Carlo calculation were made to verify the reliability of above results.FindingsThe gas flow mechanism and corresponding regulations are significantly different from traditional pneumo dynamics, which can be described by Navier–Stokes equations accurately. Combining theatrical study and computational results, the stratification theory of the gas film was verified. The research shows that when the gas flow rate increased, the pressure of the gas film decreased, the thickness of the continuous flow layer increased, the thickness of the thin layer decreased and the layered pressure in the gas film disappeared. In this case, velocity slippage could be ignored.Originality/valueFirst, this paper established an analytical model of the gas film support and proposed a film stratification theory. The gas film was divided into the near wall layer, the thin layer and the continuous layer, which was proved by the calculation of LAMMPS flow simulation. The velocity slip boundary conditions theory is feasible. Second, the gas film size of the flat plate is at the micron level, which cannot be observed in its flow regimen, only determined by calculation and simulation. This paper proposes a new model and a new tool to analyze gas flow in gas films.

Stepwise dynamics of an anionic micellar film – Formation of crown lenses

We studied the stepwise thinning of a microscopic circular foam film formed from an anionic micellar solution of sodium dodecyl sulfate (SDS). The foam film formed from the SDS micellar solution thins in a stepwise manner by the formation and expansion of a dark spot(s) of one layer less than the film thickness. During the last stages of film thinning (e.g., a film with one micellar layer), the dark spot expansion occurs via two steps. Initially, a small dark circular spot inside a film of several microns in size is formed, which expands at a constant rate. Then, a ridge along the expanding spot is formed. As the ridge grows, it becomes unstable and breaks into regular crown lenses, which are seen as white spots in the reflected light at the border of the dark spot with the surrounding thicker film. The Rayleigh type of instability contributes to the formation of the lenses, which results in the increase of the dark spot expansion rate with time. We applied the two-dimensional micellar-vacancy diffusion model and took into consideration the effects of the micellar layering and film volume on the rate of the dark spot expansion [Lee et al., 2016] to predict the rate of the dark spot expansion for a 0.06M SDS film in the presence of lenses. We briefly discuss the Rayleigh type of instability in the case of a 0.06M SDS foam film. The goals of this study are to reveal why the crown lenses are formed during the foam film stratification and to elucidate their effect on the rate of spot expansion.

Optimization procedure and fabrication of highly efficient and thermally stable solar coating for receiver operating at high temperature

In “parabolic trough” technology for concentrating solar plants, optimization and fabrication of effective and thermally stable solar coatings represent the most challenging technological goal in order to maximize the photo-thermal conversion efficiency of a solar field operating at high temperature. Starting from the typical cermet-based thin film stratification constituting high-performance solar coating, the optical properties of the metallic layer deposited as “back reflector” strongly determines the thermal loss amount, where solar coating emissivity should have to be as low as possible. Thanks to its very high reflectance in the infrared region, silver is more promising respect to transition metals such as molybdenum and tungsten. An adaptive tungsten layer deposited on stainless steel substrate has been employed with the aim of promoting improvements both on adhesion and on thermal stability of the Ag infrared reflector. Optimization procedure has been in detail described to design and to realize effective cermet-based solar coatings. Six different solar coatings with Ag as back reflector have been optically designed by means of a semi-empirical procedure where a layer-on-layer ellipsometric characterization was utilized. These optimized coatings were fabricated at increasing solar absorptance values coupled with emissivity values, evaluated at 580°C, lower than 14%. Improved performances have been obtained respect to similar optimized solar coatings with W as back reflector and the highest photo-thermal conversion efficiency has been reached (>92% at 400°C and >85% at 550°C) among the solar coatings at the present state of the art. Excellent thermal and optical stability has been proved by means of annealing cycles at 580°C under vacuum for a total duration of 85 days.

Stratification of a Foam Film Formed from a Nonionic Micellar Solution: Experiments and Modeling

Thin liquid films containing surfactant micelles or other nanocolloidal particles are considered to be the key structural elements of foams containing gas and liquid. We report here the experimental results and theoretical modeling for the phenomenon of the stratification (stepwise thinning) of a foam film formed from a nonionic micellar solution. The film stratification phenomenon was experimentally observed by reflected light microinterferometry. We observed that the stepwise layer-by-layer decrease of the film thickness is due to the appearance and growth of a dark spot of one layer less than the film thickness in the film. The dark spot expansion is driven by the diffusion of the dislocation (or vacancy) in the micellar lattice. The vacancies from the meniscus diffuse and condense into the dark spot, leading to its expansion inside the film. We experimentally observed the expansion of the dark spot at various film thicknesses (i.e., the number of micellar layers) and at different film sizes. We also measured the contact angle between the film and the meniscus; we used the data to estimate the structural film interaction energy barrier and the apparent diffusion coefficient. We used the two-dimensional diffusion model to model the dynamics of the dark spot expansion with consideration to the apparent diffusion coefficient and the film size. The model predictions are in good agreement with the experimental observations. On the basis of this model, we carried out a parametric study depicting the effects of the film thickness (or the number of micellar layers) and film area on the rate of the dark spot expansion. We also generalized the model previously proposed by Kralchevsky et al. [ Langmuir 1990 , 6 , 1180 - 1189 ], incorporating the effects of the film size, film thickness, and apparent diffusion coefficient to predict the dark spot expansion rate.

Experimental evidence of ultrathin polymer film stratification by AFM force spectroscopy

By performing Atomic Force Microscopy measurements of pull-off force as a function of the temperature, we were able to probe the dynamic of supported thin polystyrene (PS) films. Thermal transitions induce modifications in the surface energy, roughness and surface modulus that are clearly detected by AFM and related to PS chain relaxation mechanisms. We demonstrated the existence of three transition temperatures that can be associated to the relaxation of polymer chains located at different depth regions within the polymer film. Independently of the film thickness, we have confirmed the presence of a region of high mobility for the polymer chains at the free interface. The thickness of this region is estimated to be above 7nm. The detection of a transition only present for film thicker than the gyration radius Rg is linked to the dynamics of polymer chains in a bulk conformation (i.e. not in contact with the free interface). We claim here that our results demonstrate, in agreement with other techniques, the stratification of thin polymer film depth profile in terms of relaxation behavior.

Morphological origin for the stratification of P3HT:PCBM blend film studied by neutron reflectometry

Understanding the origin for the film stratification of electron donor/acceptor blend is crucial for high efficiency organic photovoltaic cell. In this study, P3HT:PCBM blend is deposited onto hydrophilic and hydrophobic substrate to examine the film stratifications. The neutron reflectivity results show that, on the different surfaces, PCBM diffuses toward the two interfacial regions in an identical fashion during thermal annealing. This evidences that the film stratification is not affected by the substrates. Instead, since P3HT remains more amorphous in the interfacial regions and PCBM is miscible with amorphous P3HT, PCBM preferentially diffuses to the interfacial regions, resulting in the stratification.

Controlled nanostructuration of polycrystalline tungsten thin films

Nanostructured tungsten thin films have been obtained by ion beam sputtering technique stopping periodically the growing. The total thickness was maintained constant while nanostructure control was obtained using different stopping periods in order to induce film stratification. The effect of tungsten sublayers' thicknesses on film composition, residual stresses, and crystalline texture evolution has been established. Our study reveals that tungsten crystallizes in both stable α- and metastable β-phases and that volume proportions evolve with deposited sublayers' thicknesses. α-W phase shows original fiber texture development with two major preferential crystallographic orientations, namely, α-W⟨110⟩ and unexpectedly α-W⟨111⟩ texture components. The partial pressure of oxygen and presence of carbon have been identified as critical parameters for the growth of metastable β-W phase. Moreover, the texture development of α-W phase with two texture components is shown to be the result of a competition between crystallographic planes energy minimization and crystallographic orientation channeling effect maximization. Controlled grain size can be achieved for the α-W phase structure over 3 nm stratification step. Below, the β-W phase structure becomes predominant.

Macro-to-microchannel transition in two-phase flow: Part 1 – Two-phase flow patterns and film thickness measurements

The classification of macroscale, mesoscale and microscale channels with respect to two-phase processes is still an open question. The main objective of this study focuses on investigating the macro-to-microscale transition during flow boiling in small scale channels of three different sizes with three different refrigerants over a range of saturation conditions to investigate the effects of channel confinement on two-phase flow patterns and liquid film stratification in a single circular horizontal channel (Part 2 covers the flow boiling heat transfer and critical heat flux). This paper presents the experimental two-phase flow pattern transition data together with a top/bottom liquid film thickness comparison for refrigerants R134a, R236fa and R245fa during flow boiling in small channels of 1.03, 2.20 and 3.04 mm diameter. Based on this work, an improved flow pattern map has been proposed by determining the flow patterns transitions existing under different conditions including the transition to macroscale slug/plug flow at a confinement number of Co ≈ 0.3–0.4. From the top/bottom liquid film thickness comparison results, it was observed that the gravity forces are fully suppressed and overcome by the surface tension and shear forces when the confinement number approaches 1, Co ≈ 1. Thus, as a new approximate rule, the lower threshold of macroscale flow is Co = 0.3–0.4 while the upper threshold of symmetric microscale flow is Co ≈ 1 with a transition (or mesoscale) region in-between.

Behaviour of wetting films of sodium hyaluronate saline solutions

The behaviour of wetting films of sodium hyaluronate (NaHA) saline solutions, at physiological conditions, is investigated using interferometry. Concentrations in the range of dilute and semi-dilute regimes were chosen to assess the role of bulk molecular interactions on the surface forces. The transition from dilute to semi-dilute solutions is known to occur at c ∗ = 0.59 mg mL −1 . Dilute solutions form stable films whose behaviour is explained by van der Waals interactions. For semi-dilute solutions, the disjoining pressure vs film thickness isotherms show branches attributed to stepwise thinning or film stratification, which is interpreted in terms of a network as predicted by the theory of semi-dilute polyelectrolyte solutions. The distance between branches is 16 nm for the NaHA concentration of 2 mg mL −1 and 12 nm for the concentration of 3.5 mg mL −1, in agreement with the calculated correlation lengths of the polymeric network. Since no experimental evidence exists for the presence of a stable network in the bulk, this tendency for self-association should be the result of the liquid confinement. To our knowledge, the existence of oscillatory disjoining pressure isotherms in the presence of excess salt was never observed for other polyelectrolyte solutions.

Colloidal Particle Morphology and Film Formation; the Role of Bio-Active Components on Stimuli-Responsive Behavior

Colloidal dispersions stabilized by biologically active dispersing agents such as phospholipids have become of significant interest due to the ability of manipulating polymer morphologies through tailoring synthetic and surface properties. As a result, unique particle morphologies ranging from hollow, cocklebur, and tubular shapes can be obtained. This review outlines recent advances in this field and discusses the role of bioactive phospholipids on generation these morphologies as well as film formation processes. Various possibilities and opportunities resulting from stimuli-responsive film formation and stratification processes stimulated by solution ionic strength, pH, enzyme concentration, and temperature are discussed. The control stratification and mobility during and after coalescence are the key factors in developing lipid rafts. Stimuli-responsive behaviors of colloidal films, if accurately controlled, offer a number of opportunities in their utilization for medical, sensing, and other devices.

Aqueous foam films stabilized by sodium naphthenates

Stratification of a foam liquid film drawn from aqueous solutions of sodium naphthenate at relatively high concentration is likely due to a lamellar liquid crystal-like structure within the film. Film stratification, resulting in stepwise thinning, has been observed in foam films formed from systems containing either moderate to high concentrations of surfactant or in films formed from solutions containing solid particles. At moderate surfactant concentrations, film stratification is likely due to layers of ordered spherical micelles as postulated in Wasan and Nikolov's model of film stratification [A.D. Nikolov, P.A. Kralchevsky, I.B. Ivanov, D.T. Wasan, J. Colloid Interface Sci. 133 (1989) 13]. At high surfactant concentrations, stepwise thinning of the films and occurrence of domains of uniform color within the film suggest a lamellar liquid crystal-like structure within the film, potentially up to hundred or more oriented layers. The LLC-like structure inside the film can occur at concentrations below the lower limit of the LLC existence as a bulk phase.

Stepwise thickening in aqueous foam films stabilized by sodium naphthenates

During drainage of a foam film formed from an aqueous sodium naphthenate solution, a transient, local, stepwise thickening process was observed. Film stratification is related to the stepwise thinning drainage process where individual layers of material are drained from a film. The process typically involves the appearance of a sequence of small, uniformly thick spots that eventually expand to the size of the film. The appearance and growth of each spot represents a discrete decrease in the thickness of the film. The size of each decrease or step typically corresponds to the size of one or more lamella layers of the stratified film. Stepwise thinning was observed in a foam film formed from an aqueous sodium naphthenate solution, as frequently reported for a variety of systems. However, during the drainage process, a transient stepwise thickening process was also observed. Bright spots began to appear and grow, indicate a discrete increase in the thickness of a portion of the film. This local, stepwise thickening process appeared to be an alternate and temporary drainage process directly related to the expansion of the stepwise thinning spots.

Stratification Phenomena in Thin Liquid Films Containing Polyelectrolytes and Stabilized by Ionic Surfactants

We have investigated the oscillations of the disjoining pressure, corresponding to film stratification, for foam films containing small concentrations of ionic surfactants and carboxymethylcellulose, an anionic polysaccharide. In water, this polyelectrolyte does not form surface complexes with AOT, an anionic surfactant. However, when mixed with cationic surfactants, in this case alkyltrimethylammonium bromides (CnTAB), strong polymer−surfactant interactions create an enhanced coadsorption of both components at the air−water interface that strongly depends on surfactant concentration. We have found stratification phenomena whatever the nature of the surfactant. The oscillation period of the disjoining pressure varies with the polymer concentration as Cp-1/2, and is close to the mesh size defined for semidilute polymer solutions. However, the dynamic properties of the liquid films and their stability are in turn very sensitive to the nature of the surfactant charge, as revealed from the behavior of the str...

Stratification of foam films made from polyelectrolyte solutions

Studies of thin liquid films, made from semidilute polyelectrolyte solutions, are presented. The disjoining pressure variation with film thickness exhibits oscillations, corresponding to film stratification. The oscillations become sharper as the polymer concentration c increases, and disappear when salt is added. The period of the oscillations scales as c-1/2. The observed stratification is related to the polymer network and the size of the steps to the mesh size ξ.

Film Stratification in the Presence of Colloidal Particles

This is probably the first study about the drainage of curved liquid films in the presence of colloidal particles. The systems did not contain any surfactant. In the presence of monodispersed colloidal particles, thinning occurs in a stepwise manner (stratification). It has been shown that the size of the film is an important parameter in the stepwise thinning process. This investigation found a critical film size below which at least one layer of particles stays in the film at equilibrium; a “spot” (a thinner section of the film), even if formed, does not expand and is in equilibrium with the film. The area of the spot expands linearly with time. The rate of spot-area expansion increases linearly with the film perimeter and can be increased or decreased merely by changing the film size. The stepwise film thinning and the effects of film size and particle concentration on film stability are discussed on the basis of the diffusive-osmotic mechanism.