Drying and cracking of soft latex coatings

The minimum film formation temperature (MFFT) is the minimum drying temperature needed for a latex coating to coalesce into an optically clear, dense crack-free film. To better understand the interplay of forces near this critical temperature, cryogenic scanning electron microscopy (cryoSEM) was used to track the latex particle deformation and water migration in coatings dried at temperatures just above and below the MFFT. Although the latex particles completely coalesced at both temperatures by the end of the drying process, it was discovered that particle deformation during the early drying stages was drastically different. Below the MFFT, cracks initiated just as menisci began to recede into the packing of consolidated particles, whereas above the MFFT, partial particle deformation occurred before menisci entered the coating and cracks were not observed. The spacing between cracks measured in coatings dried at varying temperatures decreased with decreasing drying temperature near the MFFT, whereas it was independent of temperature below a critical temperature. Finally, the addition of small amounts of silica aggregates was found to lessen the cracking of latex coatings near the MFFT without adversely affecting their optical clarity.     

Process model for latex film formation: Optical clarity fronts

We examined the drying behavior of latex both theoretically and experimentally. The theory extends a model for horizontal drying fronts in films with nondeformable particles to incorporate particle deformation by a capillary deformation mechanism. The pressure in the fluid, causing particle compaction, arises from flow through the packed bed to ensure evaporation from all wet areas of the film. We predicted the position of a front of volume fraction unity passing across a semi-infinite film as it dries. Experimentally, the position of the transition from a cloudy film to optical clarity was tracked visually in films comprised of either single component soft latex particles, 20°C above the glass transition, or a blend containing 35% non-deformable hard latex particles. For an initial volume fraction of 0.33, we found excellent agreement between theory and experiment. For an initial volume fraction of 0.05, the agreement is less, although still qualitative. The limitations of the model with respect to the knowledge of physical parameters and initial conditions are discussed. One major implication of the model is that deformation of soft latex particles displaces large amounts of water and, consequently, slows progression of the drying front. Harder particles and shallow initial film profiles produce more pronounced drying fronts. Dept. of Chemical Engineering, Princeton, NJ 08544. Emulsion Polymers Institute and Dept. of Chemical Engineering, Bethelhem, PA 18015.     

DRYING OF LATEX FILMS OF POLY(VINYL ACETATE)

ABSTRACT

Drying of Poly(vinyl acetate) latex films has wide application in the industries of synthetic fibers, adhesives, coatings, paints, etc. In this investigation, drying of Poly(vinyl acetate) latex film was studied experimentally in a drying tunnel where the air velocity and temperature were controlled. The water evaporation rate was obtained by weighing the latex film during the drying process. The weight loss of latex was measured for different polymer concentrations, film thicknesses, drying areas, temperatures, and air velocities. Results emphasize the important role of these parameters on the relative water transport from the latex film. Increasing air velocity and temperature leads to a significant increase of the weight loss of latex and drying rate. Changing other parameters affects only the rate of weight loss but not the constant drying rate.     

HEAT AND MASS TRANSFER DURING SAPWOOD DRYING ABOVE THE FIBRE SATURATION POINT

Pine sapwood was dried in an air convection kiln at temperatures between 60-80 °C. Temperature and weight measurements were used to calculate the position of the evaporation front beneath the surface. It was assumed that the drying during a first regime is controlled by the heat transfer to the evaporation front until irreducible saturation occurs. Comparisons were made with CT-scanned density pictures of the dry shell formation during initial stages of drying of boards.

The results indicate a receding evaporation front behaviour for sapwood above approximately 40-50% MC when the moisture flux is heat transfer controlled. After that we finally reach a period where bound water diffusion is assumed to control the drying rate.

The heat transfer from the circulating air to the evaporation front controls the migration flux. In many industrial kilns the heating coils therefore have too small heat transfer rates for batches of thin boards and boards with high sapwood content.     

DRYING OF LATEX FILMS OF POLY(VINYL ACETATE)

Drying of Poly(vinyl acetate) latex films has wide application in the industries of synthetic fibers, adhesives, coatings, paints, etc. In this investigation, drying of Poly(vinyl acetate) latex film was studied experimentally in a drying tunnel where the air velocity and temperature were controlled. The water evaporation rate was obtained by weighing the latex film during the drying process. The weight loss of latex was measured for different polymer concentrations, film thicknesses, drying areas, temperatures, and air velocities. Results emphasize the important role of these parameters on the relative water transport from the latex film. Increasing air velocity and temperature leads to a significant increase of the weight loss of latex and drying rate. Changing other parameters affects only the rate of weight loss but not the constant drying rate.     

HEAT AND MASS TRANSFER DURING SAPWOOD DRYING ABOVE THE FIBRE SATURATION POINT

ABSTRACT

Pine sapwood was dried in an air convection kiln at temperatures between 60-80 °C. Temperature and weight measurements were used to calculate the position of the evaporation front beneath the surface. It was assumed that the drying during a first regime is controlled by the heat transfer to the evaporation front until irreducible saturation occurs. Comparisons were made with CT-scanned density pictures of the dry shell formation during initial stages of drying of boards.

The results indicate a receding evaporation front behaviour for sapwood above approximately 40-50% MC when the moisture flux is heat transfer controlled. After that we finally reach a period where bound water diffusion is assumed to control the drying rate.

The heat transfer from the circulating air to the evaporation front controls the migration flux. In many industrial kilns the heating coils therefore have too small heat transfer rates for batches of thin boards and boards with high sapwood content.     

Film formation from monodisperse acrylic lattices: Part 3: Drying and ageing of acrylic latex films

The influence of drying/ageing on the structure and properties of acrylic latex films was investigated using turbidity measurements in combination with gravimetry, scanning electron microscopy (SEM), atomic force microscopy (AFM) and water vapour permeability. Ageing above the minimum film formation temperature (MFFT) leads to marked changes in a dried latex film, whereas, after ageing below the MFFT, changes are hardly found. Above the MFFT there is a continuous change in the film properties with time. This becomes obvious from the decreases in the regenerated interference minimum, water vapour permeability and corrugation height. The influence of ageing on the water absorption of the films is less straight forward. It was expected that films with a more compact structure would absorb less water. This is correct for short drying times only, from 0.5 to 3 h. Ageing of better-dried films, however, yields the opposite result: by increase of the ageing time from 3 to 150 h the water uptake increases. There are various reasons for this increase; they are discussed briefly.     

配合胶乳和硫化胶乳胶膜干燥历程及交联密度比较研究

采用热风干燥方法进行配合胶乳和硫化胶乳胶膜的干燥实验,研究了两种天然胶乳胶膜的千燥动力学过程及干燥过程与橡胶分子链交联密度的关系。结果表明,配合胶乳膜干燥的活化能Ea1=314kJ·mol^-1,硫化天然胶膜的干燥活化能Ea2=63．6kJ·mol^-1,配合胶乳膜较硫化胶乳膜易于干燥;在相同条件下,配合胶乳膜的交联密度始终低于硫化胶巍膜。配合胶乳膜和硫化胶乳膜的干燥过程与硫化过程并不同步,过度的加热干燥会导致交联密度的降低。     

The onset of polymer diffusion in a drying acrylate latex: how water initially retards coalescence but ultimately enhances diffusion

The diffusion of polymer chains across the interface between distinct latex particles is the final step in latex film maturation. This step drives the transformation of a honeycomb of compacted latex particles bound by weak surface forces into a mechanically robust film. Knowledge of the onset of this diffusion process is limited. We have examined film formation in butyl acrylate-methyl methacrylate copolymer latex containing 1 wt% methacrylic acid. These films dry via a propagating drying front. We were able, via fluorescence resonance energy transfer measurements, to determine the extent of polymer interdiffusion at 23°C as a function of distance from the edge of the drying front for a series of partly wet latex films. Our apparatus allows us to arrest the latex drying process and to extract interdiffusion information from sub-millimeter regions of the drying film. We have tracked the latex drying process and subsequent polymer diffusion as a function of humidity. We find that adjacent to the drying front, increasing humidity initially delays the onset of interdiffusion, but once this initial barrier is overcome increasing humidity increases the rate of diffusion. This transition occurs within 1–2 mm of the drying front.

Turbidity study of the process of film formation of thin films of aqueous acrylic dispersions

This study was directed towards determining the factors that define the process of film formation of binder particles in drying aqueous dispersion coatings, based on acrylic polymers. The work described focuses on the infrastructure of drying and ageing thin films of acrylic latices.

In concentrated latices the binder particles are arranged in closely packed structures which cause colored light patterns, the so-called Bragg diffractions. The light waves move within the latex film, where the waves are scattered by the internal structure composed of the spheres and water voids. The pattern of light transmission reveals the internal structure of the latex film. From the change in interference during the drying process of a thin latex film, it is possible to follow the internal movement and deformation of polymer spheres (coalescence process). Further coalescence results in a transparent film. When this film is immersed in water, the remaining internal interfaces between the adhered binder particles swell, thus regenerating the interference pattern. It is expected that during ageing of the film, the proportion of internal interfaces will decrease with time, so that when the aged film is immersed in water the remaining internal interfaces will swell. The resulting interference pattern reveals the decrease in the interfaces between the deformed polymer particles in the dried latex film (auto-adhesion process).     

Bimodal dispersions in coating applications

This paper describes a study of several model bimodal particle size distribution latex systems produced by blending large and small particle size anionically stabilised latices over a wide range of blend ratios. Minimum film forming temperature (MFT), drying rate, tensile and water uptake measurements were carried out. At a 80/20 weight ratio large/small particles a minimum was observed in the MFT and also in the extent of water absorption of latex films with short drying times, although for films dried for longer periods no such minimum in water absorption was observed. Drying profiles fit well with existing models, except for the 80/201/s blend which exhibits more complex drying behaviour. Low shear rate viscosity of selected blends was measured over a range of latex solids contents. The Theological data were fitted by the Krieger-Dougherty equation which was used to calculate the maximum volume packing fraction. An 80/20 blend (large/small) was found to exhibit a higher maximum volume fraction than that of either pure component of the blend, demonstrating the better packing achievable in blending. A theoretical treatment of the coalescence of bimodal particles is presented in an appendix to the paper.     

Electric conductivity measurements in water dispersion paints for mechanistic studies of reflection properties formation during surface painting and paint film drying

Electric conductivity measurements of water dispersion paints were carried out in order to understand the mechanism of film formation and drying and the formation of painted surface reflection properties. The classical model of electric conductivity in viscous media based on a comparison of the Coulomb and Stokes formulas was used to determine the effective mechanism of the paint properties. This model was verified by measurements in the paint bulk. The classical concept of the electric conductivity of viscous liquids was found to be applicable to the conductivity analysis of the studied water dispersion paint specimens. The electric conductivity of the studied paints was found to be determined by the existing admixtures being soluble in water and/or dispersion organic particles. The formulated method for dynamic conductivity measurements of paint film thickness assumed a constant temperature and viscosity. Strong electrostatic phenomena were detected at the initial stage of paint aerosol deposition, while a compact film has not been formed yet. The film conductivity measuring experiments found that the film drying process consists of two stages. At the first stage, conductivity is sharply decreasing and the paint film reflectivity is sharply increasing. At the second stage, evaporation is delayed. It is limited by the diffusion transfer of volatile components from the film bulk and from the paint dispersion particles. Here, a slow growth of the reflectivity and a decelerating decrease in the conductivity is observed. A qualitative mathematical dynamic model was developed for the paint film reflectivity due to the orientation of pigment particles, and the calculations showed that the first stage of drying is the most important for the orientation.     

基于硝酸铵气孔诱导剂的多孔TiO2薄膜的制备

采用在TiO2溶胶中加入硝酸铵的方法并通过浸渍-提拉技术制备了气孔修饰的TiO2薄膜。气孔的形成与溶胶液膜中硝酸铵诱导的分相现象相关,硝酸铵一方面抑制了干燥过程中凝结水分的挥发,另一方面增大了水相的表面张力,促使了水以球形水珠的形态分散在湿凝胶的表面,水珠挥发后形成气孔。所制备的气孔修饰的TiO2薄膜表现了超亲水性能。随着硝酸铵用量的增加,薄膜表面气孔的分布密度增大,可见光的透过率减小。增加涂膜次数可以获得多层次网络气孔结构的表面形态,多层次气孔结构的多次散射有利于提高可见光的透过性能。     

纳米氧化锌对天然胶乳膜干燥及硫化性能影响研究

采用失重法和溶胀法研究了普通氧化锌和纳米氧化锌活化的天然胶乳膜的干燥动力学,以及干燥过程中胶乳膜交联密度变化.结果表明:天然胶乳厚胶膜在成膜后仍含有大量水分并且去除困难.纳米氧化锌活化胶膜的干燥速率明显高于普通氧化锌胶膜.干燥温度对干燥过程影响显著,干燥时间随干燥温度升高明显降低.随着干燥的进行,2种氧化锌活化的胶乳膜的交联密度均迅速上升,在相同条件下,纳米氧化锌活化胶乳膜交联密度均比普通氧化锌的大.纳米氧化锌对天然胶乳膜的干燥及硫化过程均有促进作用.     

Comparative Evaluation of Hot-Air and Superheated-Steam Impinging Stream Drying as Novel Alternatives for Paddy Drying

An investigation was conducted on impinging stream drying of moist paddy using hot air and superheated steam as the drying media. Drying experiments were divided into two parts: namely, one-pass and two-pass drying. The volumetric water evaporation rate, volumetric heat transfer coefficient, and specific energy consumption of the drying system at various conditions were assessed; in the case of superheated-steam drying, the effect of steam recycle was also assessed. The quality of dried paddy was evaluated in terms of color, head rice yield, and degree of starch gelatinization. In the case of one-pass drying, an increase in the drying temperature led to a significant increase in the volumetric water evaporation rate and volumetric heat transfer coefficient. On the other hand, in the case of two-pass drying, an increase in the drying temperature led to a significant decrease in the volumetric heat transfer coefficient; the volumetric water evaporation rate was not significantly affected, however. The specific energy consumption decreased with an increase in the drying temperature. At the same temperature, using superheated steam as the drying medium led to lower specific energy consumption; higher level of steam recycle also led to more energy conservation. The color of the dried paddy was not affected by the change in the drying temperature; superheated-steam-dried paddy was redder and more yellow than the hot-air-dried paddy. An increase in the drying temperature led to decreased percentage of head rice yield. Superheated-steam drying helped enhance the level of starch gelatinization in comparison with hot-air drying at the same temperature. Nevertheless, drying at the highest tested temperature led to a lower level of starch gelatinization.     

Role of particle size on latex deformation during film formation

The ability of latex particles to deform and coalesce to form an integral film upon drying is an important property in many latex coating applications. Many theories have been proposed to account for the origin of the deformation forces. The capillary forces which depend inversely on particle size have been accepted as important for latex deformation and film formation. The minimum film forming temperature (MFFT) has been found to be a function of the particle size of latexes and has been used as evidence that the capillary forces are responsible for film formation. In this study, the deforming force at MFFT has been determined from the moduli of water-equilibrated latex polymers. No particle size dependence was observed. The magnitude of the deforming forces was at least an order of magnitude lower than that predicted by the capillary force theory. Electron microscopy of film formed below the MFFT, a condition that corresponds to early stage film formation, showed significant deformation, indicating that at the beginning of film formation, forces of magnitude predicted by the capillary force theory are present. However, the magnitude of the forces decreases rapidly as film formation progresses. The MFFT particle size dependency can be explained by the difference in the degree of water plasticization. Evidence that latexes of different particle size were plasticized by water to different extents was determined from the T_gs of the latex emulsions. Presented at the 76th Annual Meeting of the Federation of Societies for Coalings Technology, on October 15, 1998, in New Orleans, LA. Emusion Polymers Research 1604 Building, Midland, MI 48674.     

Using a new diffusivity model to accelerate the drying of biopolymer films

A model was developed to study the drying rate of biopolymer films. The diffusivity of water in this biopolymer film is an exponential function of the water concentration. This creates a situation where simply increasing gas velocity can decrease the actual drying rate. The model revealed that the main factor limiting the drying of the biopolymer film was a significant and rapid decrease in the diffusivity of water through the film as the film dried. To avoid this a pulsing scheme was proposed where the velocity of the drying gas would be varied during the experiment; this variation allowed for a compromise between a high overall drying rate and maintaining a high diffusivity within the film. It was found that the optimum combination of gas velocities was 0.8 and 0.6 m/s with a duration of 10 min at the high and low gas velocities.     

Effect of sintering on surface chemistry and surface energy of pigmented latex coatings

Drying in the absence of water (sintering) of pigmented coatings made of styrene–butadiene (SB) latex and kaolin clay at different levels of pigmentation was investigated. As found from X-ray photoelectron spectroscopy, sintered coatings showed a higher SB area percent on the surface than did latex with a high glass-transition temperature (T_g) and dried at room temperature. This was a result of latex spreading at the surface. Sintering the high-T_g coatings that were dried at room temperature caused a decrease in the surface energy. Drying in the presence of water (wet coalescing) was compared to drying in the absence of water (sintering). Even though sintered coatings were more porous and had higher gloss, no significant difference was found in the SB/clay ratio at the surface or in the surface energy above the critical pigment volume concentration (CPVC). However, at and below CPVC, the sintering process yielded a higher SB content at the surface and a lower surface energy than the wet-coalescing process. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 968–975, 2001     

Stress development and film formation in multiphase composite latexes

Designed appropriately, multiphase soft-core/hard-shell latex particles can achieve film formation without the addition of a coalescing aid, while preserving sufficient film hardness. Achieving optimal performance in these materials requires an understanding of how particle morphology affects film formation and stress development in the film. In this study, soft-core/hard-shell latex particles with different shell ratios, core and shell glass transition temperatures (T _gs), and particle sizes (63–177 nm) were synthesized using a two-stage emulsion polymerization. The film formation behavior of the composite particles was investigated with cryogenic scanning electron microscopy, atomic force microscopy, and measurements of the minimum film formation temperature (MFFT). Results show that film formation was enhanced for particles with thinner hard shells, smaller particle size, and a smaller difference in T _g between the core and shell polymers. For example, the MFFT decreased and the particle deformation increased for particles with thinner shells and smaller particle sizes. Stress development during drying was characterized using a cantilever beam bending technique. A walled cantilever design was used to monitor stress development without the complication of a lateral drying front. The film formation behavior and stress development correlated well with practical paint properties like scrub resistance and gloss.     

Delamination behavior of lithium-ion battery anodes: Influence of drying temperature during electrode processing

One essential process step during electrode processing for lithium-ion batteries is the drying of the wet particulate electrode coating. The electrode film solidifies during evaporation of the solvent and a porous film is formed. In this study, we focus on the influence of drying temperature on the internal electrode structure of the dry film. Anode slurries that consist of graphite and an aqueous binder system were coated and subsequently dried. To assure defined and controllable drying conditions, a laboratory set-up with a temperature-controlled substrate carrier and an impingement dryer was used. To facilitate a scale-up to continuously passed dryers, the choice of experimental temperatures was based on a calculation of steady-state temperatures that result from gas temperatures that are commonly applied in industrial drying processes. The delamination behavior of the differently dried electrodes was investigated by means of a 90° peel test. The results show a strong dependency of electrode adhesion on drying temperature. A lower adhesion force at higher temperatures hints at a variation in binder content at the interface between the copper substrate and the coating layer. The formation of a consolidation layer at the air-film interface during drying is identified as a possible explanation and a criterion for consolidation layer formation is suggested.