On the role of colloidal crystal-like domains in the film forming process of a carboxylated styrene-butadiene latex copolymer

Environmental scanning electron microscopy (ESEM) was employed to study the mechanism of film formation of a carboxylated styrene-butadiene latex copolymer with a glass transition temperature (T_g) of 6 °C. ESEM allows the investigation of wet samples in their native state which is required to study the drying process of latex dispersions. The film forming process was tracked by time-dependent ESEM monitoring of the latex particle morphology and by observing the different stages occurring during the drying process. The focus of our study was an analysis of the three-dimensional (3D) arrangement of the latex particles and a comparison of their appearance on the surface and in the center of the coalesced film. It was found that in the course of film formation, the latex particles arrange in domains which are similar to colloidal crystals. Such domains occur at the stage of dense particle packing. Particle coalescence appears to begin first in these domains before a continuous and homogeneous film is formed which then spreads across the entire substrate. The results suggest that for our carboxylated styrene-butadiene copolymer the current model known for the film forming mechanism which includes four main steps should be complemented by two additional ones, namely the arrangement of particles in crystal-like domains and the beginning of coalescence within these domains. This specific behavior only occurs for monodisperse latices.     

Evaporation of hydrogen peroxide with a microstructured falling film

A microstructured falling film evaporator made out of AlMg3 was used to evaporate a 50 wt.% aqueous hydrogen peroxide solution. Sufficient wetting with contact angles lower than 20° and a stable falling film was reached by a sealing procedure at elevated temperatures (about 100 °C). After a self-passivation procedure under operation conditions the relative decomposition related to the evaporated amount could be reduced to values of about 10%. From the experimental results it was concluded that the decomposition occurs mainly in the liquid phase during evaporation and not in the vapour phase by contacting the non-wetted surfaces of the evaporator and pipes. At an operation temperature of 130 °C 10 vol.% of hydrogen peroxide in the vapour could be reached which almost corresponds to the vapour/liquid equilibrium at the top of the evaporator.     

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.

Film formation of monodispersed polystyrene latex at high temperature

This report discusses the drying behavior of monodispersed polystyrene latex at elevating temperature with particular attention to the relationship between water evaporation rate and morphological evolution during the film formation process. At the first stage, water evaporation rate was less influenced by the skin film formed at the latex/air interface, which was consistent with Croll's model. During this stage, a drying front advanced from the top film toward the bulk dispersion. At the final stage of film formation, the water evaporation rate was less than that of the initial stage, and another drying front developed from the interior region outside the system. Two distinct boundaries corresponding to the opposite directions of the second drying front between completely dried region and wet region were found if the film was peeled off the container surface. Besides, some particular morphologies were found in the completely dried region, which was likely related to preferable coalescence among the particles induced by capillary force because of water evaporation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1835–1840, 2001     

Transparent,conductive polymer blend coatings from latex-based dispersions

Flexible, transparent and conductive polymer blend coatings were prepared from aqueous dispersions of poly(3,4-ethylenedixoythiophene)/poly(styrenesulfonate) [PEDOT/PSS] gel particles (∼80 nm) and latex (∼300 nm). The stable dispersions were deposited as wet coatings onto poly(ethylene terephthalate) substrates and dried at 80 °C. Microstructure studies using tapping mode atomic force microscopy (TMAFM) indicate that a network-like microstructure formed during drying at 0.03 volume fraction PEDOT/PSS loading. In this network-like structure, the PEDOT/PSS phase was forced into the boundary regions between latex. In addition, migration of the PEDOT/PSS particles towards coating surface is likely during drying of the aqueous dispersions. The addition of a small amount of dimethyl sulfoxide (DMSO) in dispersions altered the distribution of the PEDOT/PSS phase. As PEDOT/PSS concentration increases to 0.15 volume fraction, the coating surface is dominated by the PEDOT/PSS phase. The effect of DMSO on microstructure becomes less apparent as PEDOT/PSS concentration increases. The conductivity of the polymer blend coatings increases in a percolation-like fashion with a threshold of ∼0.02 volume fraction PEDOT/PSS. The addition of DMSO in dispersions enhanced the coating conductivity beyond the threshold by more than two orders of magnitude. The highest conductivity, ∼3 S/cm, occurs at 0.20 volume fraction PEDOT/PSS concentration. The polymer blend coatings have good transparency with only a weak dependence of transparency on wavelength due to the small refractive index difference between filler and matrix.     

A new direct coagulation casting process for alumina slurries prepared using poly(acrylate) dispersant

Direct coagulation casting (DCC) of concentrated aqueous alumina slurries prepared using ammonium poly(acrylate) dispersant has been studied using MgO as coagulating agent. Addition of small amounts of MgO increased the viscosity of the concentrated alumina slurries with time and finally transformed it in to a stiff gel. Sufficient working time for degassing and casting could be achieved by cooling the slurries to a temperature of ∼5 °C after proper homogenization after the addition of MgO. The DCC slip with alumina loading in the range of 50–55 vol% showed relatively low viscosity (0.12–0.36 Pa s at shear rate of 93 s⁻¹) and yield stress (1.96–10.56 Pa) values. The wet coagulated bodies prepared from slurries of alumina loading in the range of 50–55 vol% had enough compressive strength (45–211 kPa) for handling during mould removal and further drying. The coagulated bodies prepared from slurries of alumina loading in the range of 50–55 vol% showed linear shrinkage in the range of 4.8–2.3 during drying and 17.1–16.2 during sintering respectively. Near-net-shape alumina components with density >98% TD could be prepared by the DCC process.     

Effect of a coalescing aid on the earliest stages of polymer diffusion in poly(butyl acrylate-co-methyl methacrylate) latex films

In this article we use fluorescence resonance energy transfer (FRET) to investigate how a classic coalescing aid, such as 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (Texanol?) (TX), acts on the earliest stages of polymer diffusion as the latex film is still drying. In our approach, we temporarily arrest the drying process of a partially wet latex film by sealing it in an airtight chamber previously cooled to near the latex T_g. At these conditions, we are able to effectively stop the drying process and the polymer diffusion. FRET measurements at various locations on such a sample provide us information about the mechanism operating at the initial stages of polymer diffusion as the latex film is still drying. We complete our study with FRET measurements carried out at longer aging times on predried latex films. We analyze our diffusion data in terms of free volume theory and propose a mechanism that can account for the results obtained.     

High ionic transfer of a hyperbranched-network gel copolymer electrolyte for potential electric vehicle (EV) application

Hyperbranched network-based gel copolymer electrolytes are synthesized by in situ free radical polymerization. This research is separated into two parts: the first is an investigation of modified bismaleimide oligomer (MBMI) as a free volume additive, and the second investigates the salt concentration effect on high power application. A polymer electrolyte with MBMI additive provided more free volume space, and the ionic conductivity of gel copolymer electrolytes was measured as a function of the salt concentration of lithium hexafluorophosphate (LiPF₆). The highest ionic conductivity and the lowest activation energy of hyperbranched-network gel copolymer electrolytes were determined to be 7.72 × 10⁻³ S/cm at 23 °C and 5.41 kJ/mol, respectively. Furthermore, the MBMI additive and the optimal concentration of lithium salt increased the free space for carrier ions and contributed to increasing capacity and working voltage at a high rate discharge (8C). The reliability and cycling ability of lithium polymer batteries are as good as lithium ion batteries for potential electric vehicle (EV) application.     

Lowering the percolation threshold of conductive composites using particulate polymer microstructure

The percolation thresholds of carbon black–polymer composites have been successfully lowered using particulate polymer starting materials (i.e., latex and water‐dispersible powder). Composites prepared using carbon black (CB) and commercial poly(vinyl acetate) (PVAc) latex exhibit a percolation threshold near 2.5 vol % CB. This threshold value is significantly lower than that of a comparable reference composite made from poly(N‐vinylpyrrolidone) (PNVP) solution and the same CB, which exhibits a sharp rise in electrical conductivity near 15 vol % CB. This dramatic difference in critical CB concentration results from the segregated microstructure induced by the latex during composite film formation. Carbon black particles are forced into conductive pathways at low concentration because of their inability to occupy volume already claimed by the much larger latex particles. There appears to be good qualitative agreement between experimental findings and current models dealing with conductive behavior of composites with segregated microstructures. Lack of quantitative agreement with the models is attributed to the polydispersity of the polymer particles in the latex. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 692–705, 2001     

A varistor–polymer composite with nonlinear electrical-thermal switching properties

We studied the dependence of the E–J characteristics on the sintering conditions in varistor fillers, the filler content in the polymer matrix and for different polymers and suggest a possible nonlinear electrical-thermal switching mechanism. The nonlinear coefficient and breakdown field of a sample with 100 vol.% varistor fillers sintered at 950 °C for 5 h were 12.24 and 135 V/mm, separately. A decrease in the amount of filler content in polymeric matrix or using a fortified polymer improved the electrical properties by increasing the breakdown field to the 263–964 V/mm range and decreasing the leakage current density in the 1.06 × 10⁻⁵ to 1.13 × 10⁻¹⁰ A/cm² range. This varistor–polymer composite can exhibit two nonlinearities in electrical conductivity. In the conducting state above the varistor filler breakdown, the polymer matrix reduces the conductivity, if a critical temperature is reached. Thereby the over voltage is limited by the fillers (i.e. varistor effect) and the over current is limited by the polymer matrix (i.e. positive temperature coefficient effect).     

Correlation of morphology and barrier properties of thin microwave plasma polymer films on metal substrate

The barrier properties of thin model organosilicon plasma polymers layers on iron are characterised by means of electrochemical impedance spectroscopy (EIS). Tailored thin plasma polymers of controlled morphology and chemical composition were deposited from a microwave discharge. By the analysis of the obtained impedance diagrams, the evolution of the water uptake ?, coating resistance and polymer capacitance with immersion time were monitored and the diffusion coefficients of the water through the films were calculated. The impedance data correlated well with the chemical structure and morphology of the plasma polymer films with a thickness of less than 100 nm. The composition of the films were determined by means of infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The morphology of the plasma polymer surface and the interface between the plasma polymer and the metal were characterised using atomic force microscopy (AFM). It could be shown that, at higher pressure, the film roughness increases which is probably due to the adsorption of plasma polymer nanoparticles formed in the plasma bulk and the faster film growth. This leads to voids with a size of a few tens of nanometers at the polymer/metal interface. The film roughness increases from the interface to the outer surface of the film. By lowering the pressure and thereby slowing the deposition rate, the plasma polymers perfectly imitate the substrate topography and lead to an excellent blocking of the metal surface. Moreover, the ratio of siloxane bonds to methyl-silyl groups increases which implies that the crosslink density is higher at lower deposition rate. The EIS data consistently showed higher coating resistance as well as lower interfacial capacitance values and a better stability over time for the film deposited at slower pressure. The diffusion coefficient of water in thin and ultra-thin plasma polymer films could be quantified for the smooth films. The measurements show that the quantitative evaluation of the electrochemical impedance data requires a detailed understanding of the film morphology and chemical composition. In addition, the measured diffusion coefficient of about 1.5×10⁻¹⁴ cm² s⁻¹ shows that plasma polymers can act as corrosion resistant barrier layers at polymer/metal interfaces.     

Drying processes for preparation of titania aerogel using supercritical carbon dioxide

Supercritical carbon dioxide drying was performed for the preparation of titania aerogels from sol–gel routes. The conditions of supercritical carbon dioxide drying were 313–323 K and 7.8–15.5 MPa. The solvents in titania wet gels obtained from the sol–gel routes were replaced by acetone. The titania aerogels obtained from supercritical carbon dioxide drying form needle-like structures. In supercritical carbon dioxide drying, the extraction rates of acetone from the wet gels were measured by using an on-line Fourier transform infrared spectroscope. It was found that the titania aerogels with lower cohesion were induced from the formations of homogenous phase for carbon dioxide + acetone system and the lower extraction rates of acetone. Furthermore, titania films were prepared by the depositions of the titania aerogels on ITO-coated PET substrates. The needle-like aerogels with lower cohesion derive the titania film with high surface area.     

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.     

Preparation of gel polymer electrolytes using PMMA interpenetrating polymeric network and their electrochemical performances

A gel polymer electrolyte (GPE) is prepared from polymethylmethacrylate interpenetrating polymer network, benzoyl peroxide, and 1.1 M LiPF₆/EC-DEC (1:1 vol.%). The LiCoO₂/graphite cells are prepared and their electrochemical properties were evaluated at various current densities and temperatures. The viscosity of the precursor containing 5 vol.% curable mixture is around 4.6 mPa s. The ionic conductivity of the GPE at 20 °C is around 5.8×10⁻³ S cm⁻¹. The GPE has good electrochemical stability up to 4.8 V vs. Li/Li⁺. The capacity of the cell at 1.0C rate is 82% of the discharge capacity at 0.2C rate. The capacity of the cell at −10 °C is 86% of the discharge capacity at 20 °C. Discharge capacity of the cell with GPE is stable with charge-discharge cycling.     

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.     

Effects of strain rate and temperature on compressive strength and fragment size of ZrB2–SiC–graphite composites

The quasi-static (strain rate of 10⁻⁴ s⁻¹) and dynamic compression experiments (strain rate of 200–1500 s⁻¹) of ZrB₂–SiC–graphite composites are conducted at 293 K and 1073 K. The initial compressive strength and Weibull modulus are calculated to handle the discrete quasi-static experimental data. Considering effects of strain rate and temperature, the compressions of ZrB₂–SiC–graphite composites are investigated. The results show that both compressive strength and fragment size are higher at 1073 K than those at room temperature. The compressive strengths increase with increasing strain rate at room temperature and 1073 K, whereas fragment sizes decrease. Moreover, a micromechanical model is utilized to characterize the effect of strain rate on the compressive strength. The predictions of this micromechanical model are good agreement with the experimental results. Meanwhile, the fragment sizes of dynamic compressive specimens are analyzed through analytical approaches.     

Free volume behavior in spincast thin film of polystyrene by energy variable positron annihilation lifetime spectroscopy

Free volume behavior in polystyrene thin films with thickness ranging from 22 to 1200 nm on silicon substrates was studied by energy variable positron annihilation lifetime spectroscopy (EVPALS). The films were prepared by spincasting from toluene solutions of 0.5-5.0 wt% polystyrene with M_w = 1?090?000 g/mol. Distinct deviations from bulk polystyrene in thermal expansion of the free volume holes and the glass transition temperature associated with free volume behavior were observed for the thinnest film with 22 nm thickness, indicating its exclusively high chain mobility. Comparison of the polystyrene concentration in the precursor solution around the overlap concentration suggests that the high chain mobility is due to less entangled chains caused by rapid removal of the solvent from the diluted solution in order to prepare very thin film.     

Kinetic modeling of a triarylmethane dye decolorization by photoelectro-Fenton process in a recirculating system: Nonlinear regression analysis

The treatment of C.I. Acid Blue 5 solution by electrochemical process was studied under recirculation mode with a cathode containing multi walled carbon nanotubes in the presence of sodium sulfate electrolyte. Comparison of electro-Fenton and photoelectro-Fenton processes at pH 3.0 revealed that 23.04 and 98.25% of the dye was decolorized at 60 min, respectively. The kinetic of dye removal by photoelectro-Fenton process was studied with nonlinear regression analysis. A kinetic model was developed for estimation of pseudo-first order rate constant (k_app) as a function of operational parameters including initial concentration of the dye (10–50 mg/L), flow rate (5–20 L/h), pH (3–9), initial concentration of Fe³⁺ (0.05–0.2 mM) and applied current (0.05–0.45 A). The calculated results, which were obtained from kinetic model, were in consistent with the experimental data (R² = 0.9934). The calculated and experimental data were applied for prediction of the electricity consumption in decolorization processes.     

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)

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.