Film formation from monodisperse acrylic latices 5. Drying and ageing in coalescing agent containing latex films

The influences of drying temperature, ageing time and ageing temperature on the film formation in coalescing agent containing latex films were investigated via turbidity measurements and atomic force microscopy. Coalescing agents used are 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (TEX) and ethylene glycol monobutyl ether (EB). Latex films were dried at different temperatures. At a drying temperature of 40 degrees C, the differences in immersion patterns of neat and 1% coalescing agent containing latex films are too small to show significant improvement in film formation during 1 h of drying. Increase of the temperature from 40 to 50 degrees C, however, causes an improvement in film formation. At higher temperatures (95 degrees C), fast removal of the liquid phase cannot be prevented by the addition of 1% coalescing agent. Although addition of higher amounts of coalescing agent results in an increase of particle deformation and film surface smoothness, it intensifies also the water absorption of dried films. Ageing below the MFFT does not result in a significant improvement of film formation in the presence of 1% coalescing agent. Above the MFFT, coalescing agents act more efficiently and cause an improvement in film formation. By addition of higher amounts of coalescing agent the completion of the film formation process is delayed: for example, by the addition of 15% EB, nearly 1 year of ageing at room temperature is required for an efficient result.     

A model for the drying process during film formation in waterborne acrylic coatings

Establishing drying mechanisms during film formation in waterborne acrylic coatings is a technologically important problem, however complex, and still poorly understood. A model for the prediction of evaporation kinetics is proposed in this paper, where films are supposed to dry normally with respect to the film surface, and a drying front separates a top dry region from a bottom wet region. The model accounts for the competition between water evaporation and particle diffusion that determines the degree of vertical homogeneity, but also for the competition between water evaporation and particle deformation that ultimately establishes the rate-determining step in film formation processes. The model was validated by performing gravimetric water-loss experiments on latexes of acrylic polymers of various composition, various particle size and stabilizing systems, under different environmental temperatures and humidity, and various initial film thicknesses in order to evaluate the effect of the different factors that can in principle influence the film formation process.     

Effect of the acrylic acid content on the permeability and water uptake of poly(styrene-co-butyl acrylate) latex films

In this contribution, a theoretical modeling of the latex film formation is presented and compared to experimental results: water vapor permeability and latex film capacitance are studied as a function of acrylic acid content in poly(styrene-co-butyl acrylate) latex films. It has been shown that both water uptake and water vapor permeability are mainly affected by film morphology which in turn is defined by intercolloidal interaction and drying rate.     

Film formation from pure and mixed latices; transient fluorescence study

A fast transient fluorescence technique was used to study latex film formation induced by organic solvent vapor. Mixtures of pyrene (P)- and naphthalene (N)-labeled and/or pure naphthalene-labeled latex films were prepared separately from poly(methyl methacrylate) (PMMA) particles. Then these pure and mixed latex films were exposed to vapor of various chloroform-heptane mixtures in seven different experiments. In both films, fluorescence lifetimes from N were monitored during vapor-induced film formation. It was observed that N lifetimes decreased as the vapor exposure time is increased. A Stern-Volmer kinetic analysis was used for low quenching efficiencies to interpret the decrease in N lifetimes. A Prager-Tirrell model was employed to obtain back-and-forth frequencies, nu, of reptating PMMA chains during latex film formation induced by solvent vapor. In both pure and mixed latex films, nu values were found to be correlated with the chloroform content in the vapor mixture. It was observed that polymer interdiffusion obeyed a t1/2 law during film formation.     

Spontaneous film formation from a polymer solution

An unusual continuous film formation process of lateral pentyloxy substituted poly(p-phenylene terephthalate)s (s-PPPT) and poly(carbonate) (PC) is observed. A liquid film of polymer solution creeps over the surface of water dropped into the polymer solution. By vaporization of the solvent a solid polymer film is formed on the water surface and can be removed. The driving force for the film formation mechanism is assumed by the reduction of the surface tension of water. Experiments verify this mechanism by increasing the film formation speed using a gas stream, by reducing the formation speed through lowering the surface tension by rinsing agents, and by lowering the solubility of the polymer. As expected, no effects are found by variation of the pH-value of water. Necessary conditions for the film formation process are: good solubility of the polar polymers in organic solvents having a high vapor pressure, complete phase separation, solution density higher than water density, and a surrounding gas phase unsaturated with solvent vapor.The thickness of the mechanically stable films is less than 0.5 m. The films are amorphous by microscopical, FT-IR, x-ray, and DTA investigations.     

Fast transient fluorescence technique (FTRF) for studying vapor-induced latex film formation

A fast transient fluorescence (FTRF) technique was used to study latex film formation induced by organic solvent vapor. Seven different films with the same latex content were prepared separately from poly(methyl methacrylate) (PMMA) particles and exposed to vapor of various chloroform-heptane mixtures in seven different experiments. Latex films were prepared from pyrene (Py)-labeled latex particles and fluorescence lifetimes of Py were monitored during vapor-induced film formation. It was observed that pyrene lifetimes decreased as vapor exposure time increased. A Stern-Volmer kinetic analysis was used for low quenching efficiencies to interpret the decrease in pyrene lifetimes. A Prager-Tirrel model was employed to obtain back-and-forth frequencies, nu, of the reptating PMMA chains during latex film formation induced by solvent vapor. nu values were found to be correlated with chloroform content in vapor mixture. It was observed that polymer interdiffusion obeyed a t(1/2) law during film formation. The results of optical transmission experiments were found to support these findings.     

Vapor-induced film formation from low-Tg particles for different solvent compositions

The photon transmission method was used to study latex film formation from poly(vinyl acetate) (PVAc) particles induced by two different solvents. Films with the same latex content were prepared from PVAc particles and exposed to vapor of ethanol-water and acetone-water mixtures in various compositions. Transmitted photon intensities, Itr, from these films increased with increasing vapor exposure time. The increase in Itr is attributed to the increase in crossing density at the polymer-polymer junction. The Prager-Tirrell model was employed to obtain the back-and-forth frequency, nu, of the reptating polymer chain during film formation induced by solvent vapor. It was observed that the produced nu values increase as the solvent content is increased for both solvents. Abilities of both solvents to form films were interpreted with the solubility parameters of the solvents and the PVAc.     

Void closure and interdiffusion processes during latex film formation from surfactant-free polystyrene particles: a fluorescence study

This study reports a steady state fluorescence (SSF) technique for studying film formation from surfactant-free polystyrene (PS) latex particles. The latex films were prepared from pyrene (P)-labeled PS particles at room temperature and annealed at elevated temperatures for 5-, 10-, 20-, and 30-min time intervals above the glass transition (T(g)) temperature of polystyrene. During the annealing processes, the transparency of the film changed considerably. Scattered light (I(sc)) and fluorescence intensity (I(0P)) from P were measured after each annealing step to monitor the stages of film formation. Evolution of transparency of latex films were monitored using photon transmission intensity, I(tr). Scanning electron microscopy (SEM) was used to detect variation in the physical structure of annealed films. Onset temperature for film formation, T(0), void closure, T(v), and healing temperatures, T(h), were determined and corresponding activation energies were measured. Void closure and interdiffusion stages were modeled and related activation energies were determined.     

Drying dip-coated colloidal films

We present the results from a small-angle X-ray scattering (SAXS) study of lateral drying in thin films. The films, initially 10 μm thick, are cast by dip-coating a mica sheet in an aqueous silica dispersion (particle radius 8 nm, volume fraction ?(s) = 0.14). During evaporation, a drying front sweeps across the film. An X-ray beam is focused on a selected spot of the film, and SAXS patterns are recorded at regular time intervals. As the film evaporates, SAXS spectra measure the ordering of particles, their volume fraction, the film thickness, and the water content, and a video camera images the solid regions of the film, recognized through their scattering of light. We find that the colloidal dispersion is first concentrated to ?(s) = 0.3, where the silica particles begin to jam under the effect of their repulsive interactions. Then the particles aggregate until they form a cohesive wet solid at ?(s) = 0.68 ± 0.02. Further evaporation from the wet solid leads to evacuation of water from pores of the film but leaves a residual water fraction ?(w) = 0.16. The whole drying process is completed within 3 min. An important finding is that, in any spot (away from boundaries), the number of particles is conserved throughout this drying process, leading to the formation of a homogeneous deposit. This implies that no flow of particles occurs in our films during drying, a behavior distinct to that encountered in the iconic coffee-stain drying. It is argued that this type of evolution is associated with the formation of a transition region that propagates ahead of the drying front. In this region the gradient of osmotic pressure balances the drag force exerted on the particles by capillary flow toward the liquid-solid front.     

Film formation from monodisperse acrylic lattices 1. Influence of concentration and layer thickness on particle ordering

The influence of concentration and layer thickness on particle ordering in polymer latex films, both open and closed, has been studied by means of rheology, microscopy and turbidimetry. Monodisperse acrylic lattices were synthesized by semicontinuous emulsion polymerization. The lattices exhibited a distinct thixotropy above a certain concentration, which is attributed to crystallization. Microscopy revealed a three-layer structure and a dependence of crystal size and crystal packing on layer thickness and layer concentration. Turbidimetry (i.e., analysis of light transmission and interference) was used to study the progress of ordering in open and closed systems. In closed films crystallization proceeds faster at higher concentrations and in thinner films. Above a sufficiently high concentration no crystallization was observed. Furthermore, an induction time was found below certain concentrations. The drying of open latex films at temperatures below the minimum film formation temperature (MFFT) was shown to proceed through five distinct stages. The drying of open films at temperatures below the MFFT was studied by analysis of the turbidity of rewetted films. A more compact structure was found in thinner films. The structure in lattices is discussed as a result of long-range and short-range ordering.     

Film formation of polymeric emulsions: Structure set-up and the pinhole effect characterized by microscopic techniques

Drying of emulsions of special polymeric core-shell latexes results in structured films and coatings with advantageous material properties. Here, we focus on so-called “container particles”, consisting of a low viscosity core with a low glass transition (poly(2-ethylhexyl methacrylate), PEtHMA), covered by a thin shell of a cross-linked rubber (poly(n-butyl acrylate), PBA). These particles can be regarded as model emulsions of reactive polymeric oils with a very high colloidal stability. The film formation of these latexes was studied by atomic force microscopy (AFM) in the tapping mode as well as by transmission electron microscopy (TEM). It is shown that the films stay nanostructured after the drying process, i. e. they exhibit both a controlled topography as well as a network superstructure originating from the characteristics of the original dispersions.

TEM allows to detect the whereabouts of the polar stabilizer. Both continous surfactant films as well as inverted micelles are found. A geometrically induced demixing phenomenon is found which enriches the polar components and might be the molecular reason for the so-called pinhole-effect, the failure of water-born coatings in contact with water.     

Role of capillary stresses in film formation

Stresses generated during film formation were deduced from the deflection of a copper cantilever coated with a drying latex. Experiments with particles of varying radii and glass transition temperatures (Tg) focused on conditions for which capillary stresses normal to the film deform the particles to close the voids. Soft particles (low Tg) formed continuous films, but hard ones (high Tg) produced fascinating arrays of cracks. For both soft and rigid particles, the lateral stresses were tensile and scaled on the surface tension divided by the particle radius. Clearly, tensile stresses in the plane of the film responsible for cracking arise from the same capillary pressure that drives compression in the normal direction. Solving the model (Routh & Russel 1996, 1999) for lateral flow of the fluid dispersion prior to close packing and deformation of the solid beyond close packing yields volume fraction, film thickness, and stress profiles for comparison with observations for both film-forming and film-cracking cases.     

The influence of sodium ethene sulphonate comonomer on the film formation process of poly(vinyl acetate) dispersions

Various latex dispersions from vinyl acetate/sodium ethene sulphonate (sodium vinyl sulphonate) copolymers, stabilised by a constant amount of Hostapal BV, a surfactant with poly(ethylene oxide) groups, were investigated by a variety of solid and liquid state nuclear magnetic resonance methods. In order to investigate the influence of sodium ethene sulphonate on the film formation process, the serum and polymer were analysed separately. The stoichiometric monomer composition of the copolymer in the aqueous phase and in the hydrophobic particles was obtained. The ionic comonomer is enriched at the particle surface via its proximity to the applied surfactant by two-dimensional exchange NMR. For investigations of the film formation process, latex dispersions were prepared and dried to form spatially homogeneous films at different defined solid contents. Depending on the chemical composition of a chosen dispersion, NMR allows the investigation of the drying process of the water. The drying process is a function of the ionic strength of the dispersion and the hydrophilicity of the polymer. It is correlated to the drying mechanism of the water within the film. A not fully dried film contains external water outside the particles, water at ionic and non-ionic groups at surfactants in the polymer water interface and, additionally, water in the swollen and mobilised polymer. The distribution of water to these environments is markedly changed by the ionic comonomer, especially close to the end of the drying process.     

Silica-surfactant-polyelectrolyte film formation: evolution in the subphase

We have previously reported that robust mesostructured films will grow at the surface of alkaline solutions containing cetyltrimethylammonium bromide (CTAB), polyethylenimine (PEI), and silica precursors. Here we have used time-resolved small-angle X-ray scattering to investigate the structural evolution of the micellar solution from which the films form, at several different CTAB-PEI concentrations. Simple models have been employed to quantify the size and shape of the micelles in the solution. There are no mesostructured particles occurring in the CTAB-PEI solution prior to silica addition; however, after the addition of silicate species the hydrolysis and condensation of these species causes the formation of mesophase particles in a very short time, much faster than ordering observed in the film at the interface. The mesophase within the CTAB-PEI-silica particles finally rearranges into a 2D hexagonal ordered structure. With the aid of the previous neutron reflectivity data on films formed at the air/water interface from similar solutions, a formation mechanism for CTAB-PEI-silica films at the air/water interface has been developed. We suggest that although the route of mesostructure evolution of the film is the same as that of the particles in the solution, the liquid crystalline phase at the interface is not directly formed by the particles that developed below the interface.     

Temperature and relative humidity dependency of film formation of polymeric latex dispersions

Thermogravimetric analysis and a synchrotron small-angle X-ray scattering technique were employed to characterize the structural evolution of a polymeric latex dispersion during the first three stages of film formation at different temperatures and relative humidities. Three intermediate stages were identified: (1) stage I*, (2) stage I**, and (3) stage II*. Stage I* is intermediate to the conventionally defined stages I and II, where latex particles began to crystallization. The change of drying temperature affects the location of the onset of ordering, whereas relative humidity does not. Stage I** is where the latex particles with their diffuse shell of counterions in the fcc structure are in contact with each other. The overlapping of these layers results in an acceleration of the lattice shrinkage due to a decrease of effective charges. Stage II* is where the latex particles, dried well above their T(g), are deformed and packed only partially during film formation due to incomplete evaporation of water in the latex film. This is because of a rapid deformation of the soft latex particles at the liquid/air interface so that a certain amount of water is unable to evaporate from the latex film effectively. For a latex dispersion dried at a temperature close to its minimum film formation temperature, the transition between stages II and III can be continuous because the latex particles deform at a much slower rate, providing sufficient surface area for water evaporation.     

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.     

Wetting properties at the surface of iota-carrageenan-based edible films

Surface properties of edible films composed of a polymeric matrix of carrageenan in association with hydrophobic material were studied by contact angle measurements. The use of this technique not only in a static mode but also in a dynamic way enables investigation of surface hydrophobicity as well as surface wettability. The absorption flux inside the material can be estimated from the wetting kinetic, which can be very useful to quickly compare water barrier efficiency of the tested films. Comparison of carrageenan films with films containing known amounts of additives enables understanding and correlation of changes of the surface properties with the nature of used additives (glycerol used as a plasticizer, glycerol monostearate used as a surfactant, and fat) and their influence on the orientation of polymer chains at the surface during film formation. Very different responses were observed from one surface of the film (film-casting-support interface) to the other (film-air interface), which could be also attributed to the influence of the support on the polymer and to macromolecular orientation during drying after casting.     

Different types of water in the film formation process of latex dispersions as detected by solid-state nuclear magnetic resonance spectroscopy

 The properties of polymer films prepared from latex dispersions are influenced by the drying or film formation process. In order to investigate this process, various systems of aqueous latex dispersions were dried until a specific solid content was reached. The samples investigated were based on vinyl acetate, vinyl acetate/ethylene and pure acrylics employing different surfactants and polyelectrolytes as stabilisers of the dispersions. The role of water in these partially dried films was investigated using ¹H and ²H solid-state NMR spectroscopy. Different types of water could be distinguished in the spectra. The drying latex films were found to contain interfacial external water, water at ionic and nonionic groups at surfactants in the polymer/water interface and also water inside the swollen polymer. These different types of water were examined separately using various NMR techniques. Received: 22 October 1999/Accepted in revised form: 19 November 1999     

Uptake and UV-photooxidation of gas-phase PAHs on the surface of atmospheric water films. 1. Naphthalene

The adsorption and photochemical reaction of naphthalene vapor at the air-water interface of water films (22 microm and 450 microm) were studied in a horizontal flow reactor. Experiments were conducted in the regime where gas-phase mass transfer resistance did not limit the uptake. The equilibrium uptake was dependent on water film thickness only below 1 microm. Bulk water-air and air-to-interface partition constants were estimated from the experiments. The equilibrium partition constant between the water film and air decreased with increasing temperature. Photochemical reaction products were isolated in the water film after exposure to UV light. Four main oxygenated products were identified (1,3-indandione, 1(3H)-isobenzofuranone (phthalide), 2H-1-benzopyran-2-one (coumarin), and 1-naphthol). The initial rates of product formation were 46 to 154% larger for the thin film (22 microm) compared to both a thick film (450 microm) and bulk aqueous phase photooxidation. The atmospheric implications of reactions in water films are discussed.     

Near‐surface structure formation in chemically imidized polyimide films

Free‐standing polyimide films are manufactured by the chemical imidization of linear, soluble polymeric precursors. The reactive solution is coated onto a heated substrate, peeled off after partial imidization, and then dried and cured as a free‐standing film. Adhesive bonds to the cast side of the final film more strongly than to the air side. Near‐surface elastic moduli of film samples were measured with a nanoindentation setup. Samples were annealed at different final temperatures. The air side of the samples annealed at 400 °C had a higher modulus of 1.4 GPa than the 0.8 GPa of the casting side. This difference diminished as the annealing temperature was raised to 460 °C. Polyamic acid and polyimide exhibit phase transitions from disordered, isotropic solutions to ordered, liquid‐crystalline states. A theoretical model of drying and curing demonstrates formation of a gradient in conversion and ordering: the air side vitrifies at a lower solvent content, lower conversion, and higher ordering; the casting side, at a greater solvent content, higher conversion, and less ordering. Subsequent high‐temperature drying and curing of the free‐standing films removes solvent, completes reaction, and nematically orders both sides. However, longer times and higher temperature annealing are needed to bring the two sides to their common equilibrium state of nematic order. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1824–1838, 2001