Spectrophotometric measurement of swelling of polymer films by very poor solvents

Solvent swelling of polymers is important for many applications, but can be difficult to measure when thin films or very poor solvents are involved. A novel spectrophotometric method is presented that is well suited for measuring swelling of thick or thin polymer films by very poor solvents. In this method, the solvent is stained with iodine, and solvent uptake is measured by observing the change in visible light absorption of the polymer using a spectrophotometer. Using this method, swelling can be accurately measured in thin (< 2 μm) polymer films and with poor solvents that cause little swelling, even water. Results are presented for PMMA films of varying molecular weights swelled by water, by water–alcohol mixtures, and by undiluted alcohols. Swelling of these films is more rapid and more Fickian than has been reported for bulk samples, probably due to differences in PMMA molecular weight and processing. The properties of the iodine–PMMA complex are also explored. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1082–1089, 2005     

Dissolution rates of poly(methyl methacrylate) films in mixed solvents

A laser interferometer has been used to measure in situ the dissolution rates of thin films of poly(methyl methacrylate) (PMMA). The most significant finding is that addition of small amounts of a low-molecular weight nonsolvent can increase the rate obtained with a higher molecular weight solvent. In this study, silicon wafers were coated with polymer (about 1 μm thick) and annealed at 155°C for 1 h. The dissolution rates were measured at 17.5, 22.5, and 27.5°C. All the mixtures contained methyl ethyl ketone (MEK) (2-butanone), as the major component. The minor component was water, methanol, ethanol, 1-propanol, 2-propanol, or ethylene glycol. Water and methanol showed the greatest effects. Both were able to increase the dissolution rate as much as two-fold. All the mixtures exhibit the same activation energy (25 kcal/mol) despite their wide differences in dissolution rate.     

A new technique for foaming submicron size poly(methyl methacrylate) particles

About 0.7–2 μm diameter poly (methyl methacrylate) (PMMA) foamed particles were prepared via thermally induced phase separation (TIPS) from a PMMA/ethanol mixture and vacuum dried. It was found that ethanol, known to be a poor solvent to PMMA, could dissolve PMMA when the temperature was over 60°C. The solubility of PMMA (M_w = 15,000 and M_w = 120,000) in ethanol was measured and was found to increase as the temperature increased. PMMA particles on the scale of submicron and single micron diameter could be precipitated from the PMMA/ethanol solution by temperature quenching. Then, since the precipitated particles contained a certain amount of ethanol, the precipitated particles could be foamed using the ethanol as a foaming agent in a vacuum drying process. Vacuum drying at temperatures slightly below the glass transition temperature of the polymer could make the particles foam. The effects of foaming temperature and the molecular weight of the polymer on the size of foamed particles were investigated. The experimental results showed that the vapor pressure and the molecular weight of the polymer are key factors determining the expandability of the micro particles. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Small molecule desorption prior to dissolution of a polymeric glass

Poly(methyl methacrylate) (PMMA) discs in various molecular weights (M_w) were prepared by free‐radical polymerization. Pyrene (Py) was introduced during polymerization as a fluorescence probe. In situ steady state fluorescence experiments were performed to monitor desorption processes in chloroform solvent. When the PMMA discs were in chloroform, desorption of Py molecules were monitored by observing the change of Py fluorescence intensity I_P. To understand the mechanism of desorption, two different experiments were carried out in the meantime. In the first experiment, the weight of swelling and dissolving PMMA discs against dissolution time was monitored. The parallel experiment was conducted by measuring fluorescence intensity I_P from the desorbing Py molecules. Then, a set of desorption experiments were performed by monitoring I_P for various discs with different molecular weight of PMMA. A Fickian diffusion model was employed to quantify the fluorescence data produced from the swelling PMMA discs to measure desorption coefficients D_d. The measured D_d values decrease as the molecular weight of PMMA is increased in the swelling glass. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 908–912, 2006     

Dissolution rates for thin films of miscible polymer blends

The dissolution rates of thin polymer films were measured and compared. Mixtures of various ratios of poly(methyl methacrylate), PMMA, and poly(p-hydroxystyrene), PPHS, were dissolved in methyl isobutyl ketone, MIBK. The polymer solutions were then spun into thin films on silicon wafers and dried. The coated wafers were immersed in an MIBK bath and the rate of dissolution was observed using laser interferometry. The results show that pure PPHS films have dissolution rates 1000 times greater than films of pure PMMA at comparable molecular weights. However, for films containing both PPHS and PMMA, a minimum dissolution rate occurs for a mixture with about 20% (by weight) PPHS. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2015–2020, 1997     

Solute transport in non‐aqueous nanofiltration: effect of membrane material

Nanofiltration experiments in methanol and ethanol were carried out for six reference components with different molecular weights (MW 228–880) and polarities (logP 0–12). The contribution of diffusion to solute transport, calculations based on results from cell diffusion experiments, was found to be only 1–7%; solute transport occurs mainly by convection. Furthermore, it was found that solute transport is influenced by solute–solvent–membrane interactions. Solvent–solute interactions (solvation) cause a different effective solute diameter in each solvent: it is smaller in ethanol than in methanol, resulting in lower rejections in ethanol than in methanol. Solute rejection increases with increasing molecular size (for components with similar polarity). Solute–membrane interactions were expressed in polarity terms and charge effects. A decrease of the rejection with decreasing solute polarity (for components with similar MW) was observed. Since non‐polar components (high logP) are exposed to smaller repulsion forces from the polymeric membrane material, the resistance against solute permeation is lower for these components. The solvent–membrane interactions were found to result in solvation of the pore wall; the degree of membrane solvation is different for each solvent. It is determined by the affinity between the solvent and the membrane, and by the molecular size of the solvent. In ethanol, hydrophilic membranes show a larger drop in solute rejection than hydrophobic membranes. The differences in solvent–membrane affinity (measured by contact angle) are much smaller for the first membranes, and therefore pore wall solvation decreases with increasing solvent size. Hydrophobic membranes have a much larger affinity for ethanol than for methanol, leading to stronger interactions, but undergo competitive forces due to the larger solvent size. Therefore, the difference in degree of solvation and effective pore diameter is less pronounced. Based on these three observed or postulated interactions, rejections of all six reference solutes in methanol and ethanol could be explained. Copyright © 2005 Society of Chemical Industry     

Differential dissolution and electron-beam lithographic sensitivity of poly(methyl methacrylate)

Photolithographic and electron-beam integrated circuit fabrication techniques rely heavily upon differences in polymer resist dissolution (development) rates to produce circuit patterns. We have applied the wide-line NMR, technique, augmented by dynamic nuclear polarization, to the measurement of polymer dissolution rates of poly(methyl methacrylate), (PMMA). At high gamma-ray exposures, we find PMMA to have dissolution rates from 2X to 1000X those of unirradiated material. The highest radiation-enhanced dissolution rates are obtained with carbon tetrachloride-based developer solutions, whereas generally lower enhanced rates are observed with 1:3 acetone or methylethylketone/isopropanol standard developer. E-beam line exposures are developed in PMMA and poly(ethyl methacrylate), PEMA, resists using similar developers for comparison. Using straight CCl₄ as a developer, e-beam lines 1-2 μ wide were developed in 3800 Å thick PEMA resist at 1 × 10^?5 C/cm² with ≤200 Å loss in unexposed resist thickness. The higher differential dissolution with CCl₄, a poorer solvent for unirradiated PMMA than acetone or MEK, is explained by decline in polarity of PMMA by radiationinduced decarboxylation.     

Effects of swelling on the viscoelastic properties of polyester films made from glycerol and glutaric acid

Viscoelastic properties have been determined for poly(glycerol‐co‐glutaric acid) films synthesized from Lewis acid‐catalyzed polyesterifications. The polymers were prepared by synthesizing polymer gels that were subsequently cured at 125°C to form polymer films. The polymers were evaluated for the extent of reaction before and after curing by Fourier transform infrared spectroscopy. They were subsequently immersed in dimethylsulfoxide, tetrahydrofuran, water, methanol, and hexane for 24 h. The amounts of solvent absorbed were monitored and recorded. Dependent up the solvent used, the polymers were able to absorb 9.5–261% of its weight. The effects of the solvent absorption on the viscoelastic properties of the polyester films were evaluated by determining their elastic modulus (G′), viscous modulus (G″), tan δG″/G′, and complex viscosity (η*) by performing oscillatory frequency sweep experiments. The elastic modulus (G′) and viscous modulus (G″) were both higher for the dry polymers than the solvent‐absorbed polymers. However, the polymer films were all higher in elastic (G′) character than viscous (G″) character. Therefore, tan δG″/G′ < 1 before and after immersion in solvents. Values for η* decreased with angular frequency for all of the polyesters tested in this study. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Measuring and modelling the transition layer during the dissolution of glassy polymer films

The technique of laser interferometry is now used routinely by the microelectronics industry for the measurement of the dissolution rates of thin polymer films. In addition to the rate of dissolution, laser interferometry can also provide quantitative information on the thickness of the transition layer between the dissolving glassy polymer and the liquid solvent. This paper describes how observed patterns of reflected light intensity may be analyzed to calculate the thickness of the transition layer for polymers that dissolve with little or no swelling. The technique requires knowledge of the shape of the concentration profile in the transition layer. However, by assuming various simple model profiles one may obtain a reasonable estimate. Experimental measurements of poly(methyl methacrylate) (PMMA) films dissolving in methylethyl ketone indicate transition layers of thicknesses 0 to 0.1 μm for PMMA of molecular weights M_w = 37,000 to 1,400,000.     

Water–alcohol separation by pervaporation through poly(amide-sulfonamide)s (PASAs) membranes

Pervaporation membranes derived from seven homopolymers of poly(amide-sulfonamide)s (PASAs) were prepared by casting 10–17% polymer solutions of N,N-dimethylacetamide. The membranes were characterized by sorption experiments, scanning electron microscope, and wide-angle X-ray diffraction. During the pervaporation of 90 wt % aqueous solution of methanol, ethanol, 1-propanol, and 2-propanol, all membranes were preferentially permeable to water, and their separation factors were mainly dependent on the molecular weight of the solvent. The exact structure of the PASAs had a profound effect on their pervaporation characteristics. Polymeric membrane based on N,N′-bis(4-aminophenylsulfonyl)-1,3-diaminopropane and isophthaloyl chloride exhibited the best selectivity factor of 1984 for a 10 : 90 (by weight) mixture of water/ethanol at 20°C. However, the permeation rates of all materials for dehydration of 90 wt % ethanol were slow in a range of 6.6–34.4 g m⁻² h⁻¹. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1113–1119, 1997     

Facile fabrication of poly(methyl methacrylate) monolith via thermally induced phase separation by utilizing unique cosolvency

Poly(methyl methacrylate) (PMMA) monoliths with a three-dimensional continuous interconnected porous structure in a single piece were fabricated via thermally induced phase separation (TIPS) by utilizing unique cosolvency toward PMMA. We found that PMMA was soluble in a mixture of non-solvents (ethanol and water) at 60 °C. Cooling the solution resulted in formation of a monolith having interconnected pores. Cross-sectional analysis using scanning electron microscopy (SEM) showed a continuous porous network with submicron-sized skeleton. The pore size of the monolith was readily controlled by varying the fabrication parameters such as the polymer concentration and molecular weight, the cooling temperature and the solvent composition. The cross-section of the monolith showed high water repellency. The PMMA monolith was also obtained in a mixture of isopropanol and water with an appropriate solvent ratio.     

Water–ethanol permseparation by pervaporation through photocrosslinked poly(vinyl alcohol) composite membranes

Water–ethanol permselectivity was investigated by pervaporation through composite membranes which were prepared by coating photocrosslinkable poly(vinyl alcohol) containing pendant styrylpyridinium group (0.86–3.93 mol %) on porous films. These membranes were water-permselective, and the selectivity was dependent on the state of membranes; namely, incorporation ratio of styrylpyridinium group on poly(vinyl alcohol), molecular weight of the base polymer, coating thickness of a photopolymer, etc. Photocrosslinkable styrylpyridinium group showed, of course, the ionic character by a pyridinium moiety to work on permseparation of water effectively as well as preventing the dissolution of membranes by crosslinking. Membranes based on the higher molecular weight poly(vinyl alcohol) (P = 1700) gave the higher permselectivity of water in general than those of lower molecular weight (P = 500) one. Swelling of the polymers reached 160%, and permeation rate through the membranes increased with the increase of swelling. Selective diffusion of water was found to take place in swelling, and to play a part in the water-permseparation through the membranes.     

Real time monitoring of latex film dissolution by UVV technique

UV–visible (UVV) technique is used for monitoring of polymer film dissolution. These films are formed from pyrene (P)‐labeled poly(methyl methacrylate) (PMMA) latex particles, sterically stabilized by poly isobutylene (PIB, Annealing of films was performed above T_g at various temperatures for 30‐min time intervals. Diffusion of solvent molecules (chloroform) into the annealed latex film was followed by desorption of PMMA chains. Desorption of P‐labeled PMMA chains was monitored in real time by the absorbance change of P in the polymer–solvent mixture. A diffusion model with a moving boundary was used to quantify real time UVV data. Diffusion coefficients of desorbed PMMA chains were measured and found to be between 2 and 0.6 × 10⁻¹¹ cm² s⁻¹ in the 100 and 275°C temperature range. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1075–1082, 2000     

Experimental Studies and Modelling of Sorption and Diffusion of Water and Alcohols in Cellulose Acetate

The sorption characteristics of water, methanol and ethanol vapours in cellulose acetate (CA) films were measured by microgravimetry. The sorption isotherms for water vapours in the CA film at different temperatures in the range 20–40°C do not obey the Flory equation over the whole water activity range. At high water activities, the sorption extent increases much faster with the water activity than it should according to the Flory approach. The isotherms over the whole water activity range can be fitted well by the ENSIC model, a new mechanistic model developed to account for the possibility of solvent cluster formation in the polymer material. Similar behaviour was observed for ethanol, which shows a lower tendency to form clusters, but higher affinity to CA. The sigmoidal shape found for the methanol sorption isotherm suggests a strong sorption on CA sites at low methanol activities. The Guggenheim–Anderson–De Boer equa-tion fitted well this isotherm. The diffusion coefficient, which was calculated from Fickian sorption kinetics at different solvent activities by curve fitting, was constant for water but increased with ethanol content in the membrane according to an exponential relationship characterized by a limit diffusion coefficient and a plasticization coefficient. The limit diffusion coefficient for water was two orders of magnitude larger than that for ethanol, but the activation energy for ethanol was twice as large. Methanol diffusion was only Fickian at a low solvent activity; the diffusion coefficient was one order of magnitude lower than that for water. © of SCI.     

Transport models for swelling and dissolution of thin polymer films

Fundamental models have been developed to describe swelling and dissolution of glassy polymer thin films. The models account for solvent penetration by either Fickian or Case II diffusion mechanims. The convective flux due to local swelling as the solvent penetrates is included. Chain disentanglement at the polymer-developer solution interface is scaled with the local solvent concentration and polymer molecular weight using reptation theory. The effective surface concentration during dissolution is estimated by applying thermodynamics of swollen networks to the entangled polymer. Swelling and dissolution of thin polymer films have direct application to microlithography. Various molecular and processing parameters affect the outcome of resist development. The utility of the models for selecting appropriate developer solvents, minimizing resist swelling, and providing a better understanding of the swelling and dissolution of resists is demonstrated.     

Curing of polyfurfuryl alcohol resin catalyzed by a homologous series of dicarboxylic acid catalysts. II. Swelling behavior and thermal properties

Polyfurfuryl alcohol (PFA), as a bio‐based resin made from lignocellulosic materials, was crosslinked using a homologous series of dicarboxylic acid catalysts consisting of oxalic, succinic, and adipic acids, which are different in their dissociation constants. Swelling behavior, thermal stability, and non‐oxidative char residue of the resulting networks were characterized as a function of the acids strength and their concentration. Swelling of the networks were investigated at room temperature in eight solvents differing in molecular size and solubility parameter. Using acetonitrile as a solvent, the swelling mechanism was explored by applying kinetic models to the swelling data. Dynamic swelling studies during 16–30 days supported non‐Fickian and anomalous diffusion mechanism in highly crosslinked samples supporting PFA chain rigidity and high crosslinking density of the networks. Polymer–solvent interaction parameter, molecular weight between crosslinks and crosslinking densities were also determined. According to the results, the extent of PFA crosslinking and non‐Fickian behavior of the swelling solvent diffusion through the networks are strongly dependent on the concentration and dissociation characteristics of the catalysts used. Thermal stability studies showed no significant differences between the compositions, up to 900 °C. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45770.     

Non‐Fickian vapor sorption kinetics in rubbery poly(dimethyl silamethylene) and the effect of radiation‐induced crosslinking

Successive sorption runs of n‐hexane vapor in supported amorphous poly(dimethyl silamethylene) films at 25°C are presented and discussed. Deviations from Fickian sorption kinetics were observed, and they were more distinct in the as‐prepared films and in the lower n‐hexane vapor pressure runs. Polymer films, γ‐irradiated to produce various degrees of crosslinking, exhibited closer conformity to Fickian sorption kinetics and enhanced diffusivity of n‐hexane vapor. These results were consistent with the presence in the as‐prepared polymer of some labile structural order (undetectable by differential scanning calorimetry or X‐ray diffraction), which tended to be eliminated by radiation‐induced crosslinking or strong swelling. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 226–230, 2005     

Study of the solvent effect on miscibility between poly(vinyl chloride) and poly(methyl methacrylate) in the solution state – viscometric measurements

In this work, the solvent effect on the miscibility between poly(vinyl chloride) (PVC) and poly(methyl methacrylate) (PMMA) in ternary polymer solutions was examined by the viscometric method. In these systems, we could understand that the used solvents, tetrahydrofuran (THF) or N,N‐dimethylformamide (DMF), mainly affect the interaction between PVC and PMMA, while prompting various miscible properties. In PVC/PMMA/THF solution, THF is a near θ‐solvent and a poor solvent for PVC and PMMA, respectively. The mixing of the tighter PMMA coils and more extended PVC coils in THF may cause the sea–island heterogeneous structure below the weight fraction of PMMA in the polymer mixture w_PMMA = 0.7, resulting in immiscible PVC/PMMA mixtures. At w_PMMA ≥ 0.7, the PVC/PMMA mixtures are relatively miscible, giving homogeneous polymer solutions. It means that the miscibility between PVC and PMMA depends on the composition of polymer mixture. However, due to the similar affinity of DMF to PVC and PMMA, PVC/PMMA/DMF solutions exhibit high miscibility between PVC and PMMA at about w_PMMA = 0.5. © 2000 Society of Chemical Industry     

Calculation of alcohol‐acetone‐cellulose acetate ternary phase diagram and their relevance to membrane formation

ABSTRACT Alcohol‐acetone‐cellulose acetate phase diagrams incorporated with methanol, ethanol, and isopropanol as nonsolvents are calculated according to a new form of the Flory–Huggins equation. Nonsolvent–cellulose acetate interaction parameters are measured by swelling experiments. Concentration‐dependent nonsolvent–solvent interaction parameters are obtained by vapor–liquid equilibrium and the Wilson equation. It is shown that alcohol is a week coagulant compared with water, and water > methanol > ethanol > isopropanol for cellulose acetate. The phase diagrams characteristic of acetone‐cellulose acetate combined with water, methanol, ethanol, and isopropanol as nonsolvents is different, which leads to the different morphological structure of a cellulose acetate membrane. The structure of a water coagulated membrane has large macrovoids from liquid–liquid phase separation. A methanol coagulated membrane has a honeycomb‐like structure from spinodal microphase separation. An ethanol or isopropanol coagulated membrane has a thicker, dense top layer from the delay time phase separation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1650–1657, 2001     

Guidelines for dryer design based on results from non‐Fickian model

In polymer solution coatings below the glass transition temperature of the pure polymer, the coating can go undergo a glass transition and develop stresses during drying. When stresses develop, a non‐Fickian model accurately describes solvent mass transport in drying polymer coatings. The non‐Fickian model includes the solvent transport due to both stress and concentration gradients. This article presents a non‐Fickian model, which predicts a lower residual solvent than does the corresponding Fickian model. We showed in an earlier article that the non‐Fickian model predicts trapping skinning (higher residual solvent under more intense operating conditions) at higher drying gas‐flow rates. In this article, the non‐Fickian model was used to investigate how the gas‐flow rate, dry film thickness, and substrate thickness affect the residual solvent for a single‐zone dryer. This work recommends guidelines for choosing gas‐flow rates, gas temperatures, and substrate thickness to minimize the residual solvent. The model predictions show that, at any gas temperature, the residual solvent is minimum at an intermediate gas‐flow rate. The trapping skinning effect is less evident in thicker coatings and substrates. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 477–486, 2003