skip to main content

Title: Modeling solvent evaporation during thin film formation in phase separating polymer mixtures
Preparation of thin films by dissolving polymers in a common solvent followed by evaporation of the solvent has become a routine processing procedure. However, modeling of thin film formation in an evaporating solvent has been challenging due to a need to simulate processes at multiple length and time scales. In this work, we present a methodology based on the principles of linear non-equilibrium thermodynamics, which allows systematic study of various effects such as the changes in the solvent properties due to phase transformation from liquid to vapor and polymer thermodynamics resulting from such solvent transformations. The methodology allows for the derivation of evaporative flux and boundary conditions near each surface for simulations of systems close to the equilibrium. We apply it to study thin film microstructural evolution in phase segregating polymer blends dissolved in a common volatile solvent and deposited on a planar substrate. Effects of the evaporation rates, interactions of the polymers with the underlying substrate and concentration dependent mobilities on the kinetics of thin film formation are studied.
Authors:
; ; ; ;
Award ID(s):
1719854 1719960
Publication Date:
NSF-PAR ID:
10074831
Journal Name:
Soft Matter
Volume:
14
Issue:
10
Page Range or eLocation-ID:
1833 to 1846
ISSN:
1744-683X
Sponsoring Org:
National Science Foundation
More Like this
  1. Doping is required to increase the electrical conductivity of organic semiconductors for uses in electronic and energy conversion devices. The limited number of commonly used p-type dopants suggests that new dopants or doping mechanisms could improve the efficiency of doping and provide new means for processing doped polymers. Drawing on Lewis acid–base pair chemistry, we combined Lewis acid dopant B(C 6 F 5 ) 3 (BCF) with the weak Lewis base benzoyl peroxide (BPO). The detailed behavior of p-type doping of the model polymer poly(3-hexylthiophene) (P3HT) with this Lewis acid–base pair in solution was examined. Solution 19 F-NMR spectra confirmed the formation of the expected counterion, as well as side products from reactions with solvent. BCF : BPO was also found to efficiently dope a range of semiconducting polymers with varying chemical structures demonstrating that the BCF : BPO combination has an effective electron affinity of at least 5.3 eV. In thin films of regioregular P3HT cast from the doped solutions, delocalized polarons formed due to the large counterions leading to a large polaron-counterion distance. At and above 0.2 eq. BCF : BPO doping, amorphous areas of the film became doped, disrupting the structural order of the films. Despite the change in structural order, thin filmsmore »of regioregular P3HT doped with 0.2 eq. BCF : BPO had a conductivity of 25 S cm −1 . This study demonstrates the effectiveness of a two-component Lewis acid–base doping mechanism and suggests additional two-component Lewis acid–base chemistries should be explored.« less
  2. Elastomers are an important class of polymers for many applications. Often, additives are added to the polymer matrix of elastomers to promote vulcanization or enhance physical or chemical properties. In this study, vapor phase infiltration (VPI) is investigated for transforming unvulcanized cis -polyisoprene (from natural rubber) into an organic/inorganic hybrid material. Specifically, we examine single-cycle infiltration with diethylzinc (DEZ) and water to form infiltrated zinc oxide species. Interestingly, low-temperature pre-heating of the cis -polyisoprene acutely affects the processes of infiltration, including diffusivity, maximum solubility, and chemical reactivity. We attribute these effects to a combination of film relaxation and oxidation. Independent of thermal pre-treatments, all infiltration processes exhibited consistent zinc oxide loading irrespective of purge time between the DEZ and water doses, indicating the presence of a strongly bound intermediate state between the DEZ precursor and the cis -polyisoprene polymer. Increasing infiltration process temperature accelerates diffusion and lowers the maximum solubility, in accordance with Fick's law and gas phase sorption equilibrium. Resulting organic–inorganic hybrid films show enhanced resistance to dissolution in toluene, a good solvent for the pure polymer.
  3. Abstract

    Extensional flow properties of polymer solutions in volatile solvents govern many industrially-relevant coating processes, but existing instrumentation lacks the environment necessary to control evaporation. To mitigate evaporation during dripping-onto-substrate (DoS) extensional rheology measurements, we developed a chamber to enclose the sample in an environment saturated with solvent vapor. We validated the evaporation-controlled DoS device by measuring a model high molecular weight polyethylene oxide (PEO) in various organic solvents both inside and outside of the chamber. Evaporation substantially increased the extensional relaxation time$$\lambda _{E}$$λEfor PEO in volatile solvents like dichloromethane and chloroform. PEO/chloroform solutions displayed an over 20-fold increase in$$\lambda _{E}$$λEdue to the formation of an evaporation-induced surface film; evaporation studies confirmed surface features and skin formation reminiscent of buckling instabilities commonly observed in drying polymer solutions. Finally, the relaxation times of semi-dilute PEO/chloroform solutions were measured with environmental control, where$$\lambda _{E}$$λEscaled with concentration by the exponent$$m=0.62$$m=0.62. These measurements validate the evaporation-controlled DoS environment, and confirm that chloroform is a good solvent for PEO, with a Flory exponent of$$\nu =0.54$$ν=0.54. Our results are the first to control evaporation during DoS extensional rheology, and provide guidelines establishing when environmental control is necessary to obtain accurate rheological parameters.

  4. Recent studies suggest chain adsorption in the melt may be responsible for a number of property changes in thin films by making correlations between the residual adsorbed layer thickness h ads ( t ) measured after a given solvent washing procedure as a function of annealing time t of the film at an elevated temperature prior to this solvent rinse. This procedure, frequently called “Guiselin's experiment”, refers to the thought experiment proposed in a 1992 theoretical treatment by Guiselin that assumed chain segments in contact with the surface are irreversibly adsorbed whereby unadsorbed chains could be washed away by solvent without disturbing the adsorbed substrate contact points in the melt. In the present work, we review this recent literature, identifying and experimentally testing a common protocol for forming adsorbed layers h ads ( t ) from solvent washing melt films. We find h ads ( t ) curves to be far less reproducible and reliable than implied in the literature, strongly dependent on solvent washing and substrate cleaning conditions, and annealing at elevated temperatures is unnecessary as densification of films sitting at room temperature makes the glassy film harder to wash off, leaving behind h ads of comparable thickness. Thismore »review also summarizes literature understanding developed over several decades of study on polymer adsorption in solution, which experimentally demonstrated that polymer chains in solution are highly mobile, diffusing and exchanging on the surface even in the limit of strong adsorption, contradicting Guiselin's assumption. Preformed adsorbed layers of different thicknesses h ads are shown to not affect the average glass transition temperature or physical aging of 30 nm thick films. In summary, a number of open questions and implications are discussed related to thin films and polymer nanocomposites.« less
  5. Ionomer polyesters have polymer backbones functionalized with charged groups that make them water-dispersible. Despite the widespread use of ionomer polymers in environmentally friendly coatings without volatile organic solvents, the fundamental understanding of their film formation properties is still limited. In the study, we deposited polyester nanofilms of brilliant structural colors and correlated the macroscale optical properties to the microscale thickness of the thin films. We found that sessile water droplets deposited on these films drive the formation of a rich variety of structures by an evaporation-induced effect of “coffee-ring erosion”. The ionomers spontaneously get partially re-dispersed in the form of nanoparticles in the sessile droplets and driven by convective evaporation flows, become redistributed in multiple colorful ring patterns. By using the structural colors as means to follow the polymer redistribution, we characterized further the coffee-ring patterns and found that the generated patterns are dictated by polymer composition but are mostly independent on molecular weight. As expected by colloidal theory, this phenomenon was suppressed in presence of electrolytes. Furthermore, we show that the integrity of these thin polyester films can be significantly improved by thermal densification without any further chemical curing.