Over the past several years, the term PFAS (per- and polyfluoroalkyl substances) has grown to be emblematic of environmental contamination, garnering public, scientific, and regulatory concern. PFAS are synthesized by two processes, direct fluorination (e.g., electrochemical fluorination) and oligomerization (e.g., fluorotelomerization). More than a megatonne of PFAS is produced yearly, and thousands of PFAS wind up in end-use products. Atmospheric and aqueous fugitive releases during manufacturing, use, and disposal have resulted in the global distribution of these compounds. Volatile PFAS facilitate long-range transport, commonly followed by complex transformation schemes to recalcitrant terminal PFAS, which do not degrade under environmental conditions and thus migrate through the environment and accumulate in biota through multiple pathways. Efforts to remediate PFAS-contaminated matrices still are in their infancy, with much current research targeting drinking water.
The toxicity and environmental persistence of anthropogenic per- and poly-fluoroalkyl substances (PFAS) are of global concern. To address legacy PFAS concerns in the United States, industry developed numerous replacement PFAS that commonly are treated as confidential information. To investigate the distribution of PFAS in New Jersey, soils collected from across the state were subjected to nontargeted mass-spectral analyses. Ten chloroperfluoropolyether carboxylates were tentatively identified, with at least three congeners in all samples. Nine congeners are ≥(CF2)7. Distinct chemical formulas and structures, as well as geographic distribution, suggest airborne transport from an industrial source. Lighter congeners dispersed more widely than heavier congeners, with the most widely dispersed detected in an in-stock New Hampshire sample. Additional data were used to develop a legacy-PFAS fingerprint for historical PFAS sources in New Jersey.
Interfaces play an important role in modifying the dynamics of polymers confined to the nanoscale. Here, we demonstrate that the distance over which an interface suppresses molecular mobility in poly(styrene) thin films can be systematically increased by tens of nanometers by controlling the chain conformation, i.e., height of loops in irreversibly adsorbed nanolayers. These effects arise from topological interaction between adsorbed and neighboring un-adsorbed chains, respectively, which increase their motional coupling to facilitate the propagation of suppressed dynamics originating at the interface, thus highlighting the ability to manipulate interfacial effects by local conformation of chains in adsorbed nanolayers.
Annealing a supported polymer film in the melt state, a common practice to relieve residual stresses and erase thermal history, can result in the development of an irreversibly adsorbed nanolayer. This layer of polymer chains physically adsorbed to the substrate interface has been shown to influence thin film properties such as viscosity and glass transition temperature. Its growth is attributed to many simultaneous interactions between individual monomer units and the substrate stabilizing chains against desorption. A better understanding of how these specific polymer-substrate interactions influence the growth of the adsorbed layer is needed, particularly given how strongly the properties of geometrically-confined polymeric systems are impacted by interfaces. Here, we use homopolymers and random copolymers of styrene and methyl methacrylate to form adsorbed layers and examine the influence of chemical composition and the resulting polymer-substrate interactions on adsorbed layer growth and structure. Ellipsometric measurements reveal a non-monotonic trend between composition and thickness of the adsorbed layers that is inconsistent with the behavior normally exhibited by random copolymers, being intermediate to their respective homopolymers. We examine this trend in terms of plateau thickness and growth kinetics at two different annealing temperatures and propose a mechanism for how different polymer-substrate interactions combine to influence adsorption when copolymer films are annealed. By introducing compositional heterogeneity, this mechanism extends the study of irreversible adsorption to complex chemistries and provides for a more general understanding of how annealing should be accounted for in the proper selection and processing of polymer thin films for applications in nanotechnology.
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