New Method to Probe the Surface Properties of Polymer Thin Films by Two-Dimensional (2D) Inverse Gas Chromatography (iGC).

Polymer-based functional surface coatings are extensively used in advanced technologies, including optics, energy, and environmental applications. Surface thermodynamic properties profoundly impact the molecular interactions that control interfacial behaviors, such as adhesion and wettability, which in turn dictate coating processes and performance. Conventionally, contact angle measurements are used to assess the surface energy of polymer films and coatings, where the wettability of a surface is assessed using probe fluids (liquid drops). However, contact angle measurement oftentimes can be nontrivial due to the roughness or chemical heterogeneity of the solid surface, as well as the potential for the liquid drop to swell or even dissolve the material being measured. Alternatively, inverse gas chromatography (iGC) is a versatile technique to measure surface thermodynamics and Lewis acid-base properties while also providing environmental control such as temperature and humidity. Despite these benefits, the application of iGC has been limited to powders or fibers, while the direct measurement of supported thin films or coatings is still a nascent area of research. This creates a challenge when using iGC as a comprehensive platform for measuring the physicochemical properties of solid surfaces. Here, we demonstrate how to effectively use iGC to characterize the surface energy of supported polymer thin films by using a two-dimensional (2D) film holder and modifying operational controls, such as the concentration range of the injected gas probe molecules. This enables the precise control of surface coverage required for analyzing samples having minimal surface area, such as thin films. Poly(methyl methacrylate) (PMMA) was employed as a benchmark to determine suitable iGC parameters and to validate our approach on polymer thin films. The seminal work presented here expands the capability of state-of-the-art iGC to embrace supported thin films (2D iGC) that could either be smooth or display texture/roughness (patterned films) as well as coatings with heterogeneous chemical/structural composition.

Thickness Dependent CO2 Adsorption of Poly(ethyleneimine) Thin Films for Direct Air Capture.

Mesoporous silica impregnated with polyethyleneimine (PEI) has been shown to be a suitable material for the direct air capture (DAC) of CO2. Factors such as CO2 concentration, temperature, and amine loading impact overall capture capacity and amine efficiency by altering diffusional resistance and reaction kinetics. When studied in the impregnated 3-dimensional sorbent material, internal diffusion impacts the evaluation of the reaction kinetics at the air/amine interface. In this work, we designed a novel tandem quartz crystal microbalance with dissipation (QCM-D) and polarization modulation infrared reflective absorption spectroscopy (PM-IRRAS) instrument. CO2 adsorption kinetics of the PEI-based amine layer in a 2-dimensional geometry were studied at a variety of film thicknesses (10 nm to 100 nm), temperatures (25 °C to 80 °C), and CO2 concentrations (5 % and 0.04 % by mole fraction). Total CO2 capture capacity increased with film thickness but decreased amine efficiency, as additional diffusional resistance for thicker films limits access to available amine sites. The capture capacity of thick films (>50 nm) is shown to be limited by amine availability, while capture of thin films (<50 nm) is limited by CO2 availability. A 50 nm PEI film was shown to be optimal for capture of 0.04 % (400 ppm) CO2. The adsorption profiles for these conditions were fitted to pseudo-first order and Avrami fractional order models. The reaction process switches between a diffusion limited reaction to a kinetic limited reaction at 80 °C when using 5 % CO2 and 55 °C when using 0.04 % CO2. These results offer accurate analysis of adsorption of CO2 at the air/amine interface of PEI films which can be used for the design of future sorbent materials.

Correlating the Diffusion of Water to Performance in Model Reverse Osmosis Polyamides with Controlled Crosslink Densities.

We systematically reduce the cross-link density of a PA network based on m-phenylene diamine by substituting a fraction of the trifunctional trimesoyl chloride cross-linking agent with a difunctional isophthaloyl analog that promotes chain extension, in order to elucidate robust design cues for improving the polyamide (PA) separation layer in reverse osmosis (RO) membranes for desalination. Thin films of these model PA networks are fully integrated into a composite membrane and evaluated in terms of their water flux and salt rejection. By incorporating 15 mol % of the difunctional chain extender, we reduce the cross-link density of the network by a factor of two, which leads to an 80 % increase in the free or unreacted amine content. The resulting swelling of the PA network in liquid water increases by a factor of two accompanied by a 30 % increase in the salt passage through the membrane. Surprisingly, this leads to a 30 % decrease in the overall permeance of water through the membrane. This conundrum is resolved by quantifying the microscopic diffusion coefficient of water inside the PA network with quasi-elastic neutron scattering. In the highest and lowest cross-link density networks, water shows strong signatures of confined diffusion. At short length scales, the water exhibits a translational diffusion that is consistent with the jump-diffusion mechanism. This translational diffusion coefficient is approximately five times slower in the lowest cross-linked density network, consistent with the reduced water permeance. This is interpreted as water molecules interacting more strongly with the increased free amine content. Over longer length scales the water diffusion is confined, exhibiting mobility that is independent of length scale. The length scales of confinement from the quasi-elastic neutron scattering experiments at which this transition from confined to translational diffusion occurs is on the order of (5 to 6) Å, consistent with complementary X-ray scattering, small angle neutron scattering, and positron annihilation lifetime spectroscopy measurements. The confinement appears to come from heterogeneities in the average inter-atomic distances, suggesting that diffusion occurs by water bouncing between chains and occasionally sticking to the polar functional groups. The results obtained here are compared with similar studies of water diffusion through both rigid porous silicates and ion exchange membranes, revealing robust design cues for engineering high-performance RO membranes.

Dephosphorylation of Y228 and Y217 and phosphorylation of Y335 in p120 catenin activate convergent extension during zebrafish gastrulation.

BACKGROUND: The cadherin-associated protein p120 catenin regulates convergent extension through interactions with cadherin proteins, Cdc42, and Rac1, as we previously showed in zebrafish (Danio rerio). Phosphorylation of p120 catenin changes the nature of its activity in vitro but is virtually unexplored in embryos. We used our previously developed antisense RNA splice-site morpholino targeted to endogenous p120 catenin-δ1 to cause defects in axis elongation probing the functions of three p120 catenin tyrosine-phosphorylation sites in gastrulating zebrafish embryos. RESULTS: The morpholino-induced defects were rescued by co-injections with mouse p120 catenin-δ1-3A mRNAs mutated at residues Y228 and Y217 to a non-phosphorylatable phenylalanine (F) or mutated at residue Y335 to a phosphomimetic glutamic acid (E). Co-injection of the complementary mutations Y228E, Y217E, or Y335F mRNAs partially rescued embryos whereas dual mutation to Y228E-Y217E blocked rescue. Immunopurification showed Y228F mutant proteins preferentially interacted with Rac1, potentially promoting cell migration. In contrast, the phosphomimetic Y228E preferentially interacted with E-cadherin increasing adhesion. Both Y228F and Y335F strongly bind VAV2. CONCLUSIONS: p120 catenin serves dual roles during gastrulation of zebrafish. Phosphorylation and dephosphorylation of tyrosine residues Y217, Y228, and Y335 precisely balance cell adhesion and cell migration to facilitate somite compaction and axis elongation.

Observation of General Entropy-Enthalpy Compensation Effect in the Relaxation of Wrinkled Polymer Nanocomposite Films.

Surface-textured polymer nanocomposite (PNC) films are utilized in many device applications, and therefore understanding the relaxation behavior of such films is important. By extending an in situ wrinkle relaxation method, we observed that the thermal stability of wrinkled PNC films, both above and below the glass transition temperature (Tg), is proportional to a film's nanoparticle (polymer grafted and bare) concentration, with a slope that changes sign at a compensation temperature (Tcomp) that is determined to be in the vicinity of the film's Tg. This provides unambiguous confirmation of entropy-enthalpy compensation (EEC) as a general feature of PNC films, implying that the stability of PNC films changes from being enhanced to becoming diminished by simply passing through this characteristic temperature, a phenomenon having evident practical ramifications. We suggest EEC will also arise in films where residual stresses are associated with the film fabrication process, which is relevant to nanotech device applications.

Thickness-Dependent Permeance of Molecular Layer-By-Layer Polyamide Membranes.

We present the thickness-dependent permeance of highly cross-linked polyamide (PA) membranes formed by a molecular layer-by-layer (mLbL) deposition process. The deposition allows for the synthesis of extremely smooth, uniform PA films of tunable thickness, which is counter to the less controlled interfacial polymerization process used commercially. The ability to control and measure the membrane thickness allows us to elucidate the relationships among network structure, transport properties, and separation performance. In this work, a series of large-area mLbL PA membranes is prepared with thickness ranging from less than 5 nm to greater than 100 nm, which can be transferred defect-free via a film floating technique onto a macroporous support layer and challenged with salt solutions. A critical thickness of 15 nm is identified for efficient desalination, and water permeance is described using a multi-layer solution diffusion model that allows for the extraction of material properties relevant to transport. Finally, the model demonstrates the existence of two distinct layers in the mLbL films, one layer comprised of a (5 to 10) nm graded or less cross-linked layer at the surface and a more densely cross-linked layer in the interior of the film. This graded layer appears inherent to the mLbL deposition process and is observed at all film thicknesses.

Grafting polysiloxane onto ultrafiltration membranes to optimize surface energy and mitigate fouling.

Conventional approaches to mitigate fouling of membrane surfaces impart hydrophilicity to the membrane surface, which increases the water of hydration and fluidity near the surface. By contrast, we demonstrate here that tuning the membrane surface energy close to that of the dispersive component of water surface tension (21.8 mN m-1) can also improve the antifouling properties of the membrane. Specifically, ultrafiltration (UF) membranes were first modified using polydopamine (PDA) followed by grafting of amine-terminated polysiloxane (PSi-NH2). For example, with 2 g L-1 PSi-NH2 coating solution, the obtained coating layer contains 53% by mass fraction PSi-NH2 and exhibits a total surface energy of 21 mN m-1, decreasing the adsorption of bovine serum albumin by 44% compared to the unmodified membrane. When challenged with 1 g L-1 sodium alginate in a constant-flux crossflow system, the PSi-NH2-grafted membrane exhibits a 70% lower fouling rate than the pristine membrane at a water flux of 110 L (m2 h)-1 and good stability when cleaned with NaOH solutions.

Water-polyamide chemical interplay in desalination membranes explored by ambient pressure X-ray photoelectron spectroscopy.

Reverse osmosis using aromatic polyamide membranes is currently the most important technology for seawater desalination. The performance of reverse osmosis membranes is highly dependent on the interplay of their surface chemical groups with water and water contaminants. In order to better understand the underlying mechanisms of these membranes, we study ultrathin polyamide films that chemically resemble reverse osmosis membranes, using ambient pressure X-ray photoelectron spectroscopy. This technique can identify the functional groups at the membrane-water interface and allows monitoring of small shifts in the electron binding energy that indicate interaction with water. We observe deprotonation of free acid groups and formation of a 'water complex' with nitrogen groups in the polymer upon exposure of the membrane to water vapour. The chemical changes are reversed when water is removed from the membrane. While the correlation between functional groups and water uptake is an established one, this experiment serves to understand the nature of their chemical interaction, and opens up possibilities for tailoring future materials to specific requirements.

Maximizing the grafting of zwitterions onto the surface of ultrafiltration membranes to improve antifouling properties.

Superhydrophilic zwitterions have been extensively exploited for surface modification to improve antifouling properties. However, it remains challenging to form layers of < 20 nm with high zwitterion content on the surfaces with different degrees of hydrophilicity. We demonstrate that amine-functionalized sulfobetaine (SBAm) can be co-deposited with dopamine on ultrafiltration (UF) membranes, leading to a thickness of 10 nm to 50 nm and an SBAm content of up to 31 mass% in the coating layers. The covalently grafted SBAm is stable underwater and improves the antifouling properties, as evidenced by the lower trans-membrane pressure required to retain targeted water fluxes than that required for the pristine membranes. The SBAm is also more effective than conventionally used sulfobetaine methacrylate (SBMA) for the zwitterion grafting on the surface to improve antifouling properties.

Entropy-driven segregation of polymer-grafted nanoparticles under confinement.

The modification of nanoparticles with polymer ligands has emerged as a versatile approach to control the interactions and organization of nanoparticles in polymer nanocomposite materials. Besides their technological significance, polymer-grafted nanoparticle (PGNP) dispersions have attracted interest as model systems to understand the role of entropy as a driving force for microstructure formation. For instance, densely and sparsely grafted nanoparticles show distinct dispersion and assembly behaviors within polymer matrices due to the entropy variation associated with conformational changes in brush and matrix chains. Here we demonstrate how this entropy change can be harnessed to drive PGNPs into spatially organized domain structures on submicrometer scale within topographically patterned thin films. This selective segregation of PGNPs is induced by the conformational entropy penalty arising from local perturbations of grafted and matrix chains under confinement. The efficiency of this particle segregation process within patterned mesa-trench films can be tuned by changing the relative entropic confinement effects on grafted and matrix chains. The versatility of topographic patterning, combined with the compatibility with a wide range of nanoparticle and polymeric materials, renders SCPINS (soft-confinement pattern-induced nanoparticle segregation) an attractive method for fabricating nanostructured hybrid films with potential applications in nanomaterial-based technologies.

Thermally Stable Cross-linked P84 with Superior Membrane H2/CO2 Separation Properties at 100 °C.

Polymers with a strong size-sieving ability and superior H2/CO2 selectivity are of great interests for pre-combustion CO capture at 100 °C or above. Polyimides (such as Matrimid® and 6FDA-durene) have been cross-linked using diamines and show superior H2/CO2 selectivity. However, these cross-linked polymers cannot be used for the pre-combustion CO2 capture because of the lack of thermal stability at 100 C. Herein we demonstrate that commercial P84™ can be chemically cross-linked using 1,4-butanediamine (BuDA) to achieve robust H2/CO2 separation properties at 100 °C to 150 °C. The cross-linked P84 were thoroughly evaluated using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The effects of the cross-linking time on the physical properties and H2/CO2 separation properties at various temperatures were determined and interpreted using a free volume model. An exemplary sample based on P84 crosslinked by BuDA for 6 h exhibits a H2 permeability of 47 Barrers (1 Barrer = 3.35 × 10-16 mol m/m2·s·Pa) and H2/CO2 selectivity of 14 at 100 °C, which is on the Robeson's upper bound, indicating their potential for practical applications.

Reduced Holey Graphene Oxide Membranes for Desalination with Improved Water Permeance.

Reduced-graphene oxide (r-GO) membranes with narrow channels exhibit salt rejections comparable to conventional nanofiltration (NF) membranes. However, their water permeances are much lower because of the high tortuosity for water permeation. Herein we report a facile solution-processable approach to create in-plane nanopores on GO nanosheets before reduction, dramatically decreasing the tortuosity and increasing water permeance while retaining the salt rejection. Specifically, holey GO (HGO) nanosheets were prepared via chemical etching using hydrogen peroxide, followed by the deposition on a porous support by vacuum filtration and then reduction via exposure to hydriodic acid solutions to generate the reduced HGO (r-HGO) membrane. The generation of nanopores increases the water permeance from 0.4 L m-2∙h-1∙bar-1 (LMH/bar) to 6.6 LMH/bar with Na2SO4 rejection greater than 98.5 %, and the membranes were robust under strong cross-flow shearing force for 36 h. Both water permeance and Na2SO4 rejection of these r-HGO membranes for the first time simultaneously reach the level of the commercial polyamide-based NF membranes. Given their good antibacterial properties and resistance to aggressive chemical washing, the r-HGO membranes show the promise as next-generation NF membranes for desalination.

Characterizing salt permeability in polyamide desalination membranes using electrochemical impedance spectroscopy.

Improving the performance of desalination membranes requires better measurements of salt permeability in the polyamide separating layer to elucidate the thermodynamic and kinetic components of membrane permselectivity. In this work, electrochemical impedance spectroscopy (EIS) is introduced as a technique to measure the salt permeability and estimate the salt partition coefficient in thin polyamide films created using molecular layer-by-layer deposition. The impedance of supported polyamide films ranging in thickness from 3.5 nm to 28.5 nm were measured in different electrolyte solutions. Impedance spectra were modeled with equivalent circuits containing resistive and capacitive elements associated with the EIS measurement system as well as characteristic low-frequency parallel resistive and capacitive elements that are associated with the polyamide film. The characteristic polyamide membrane resistance increases with film thickness, decreases with solution concentration, and is an order of magnitude greater for a divalent cationic solution than for a monovalent cationic solution. For each polyamide film, salt permeability is calculated from the membrane resistance, and a salt partition coefficient is estimated. At the highest solution concentration measured, which is representative of brackish water desalination conditions, the calculated salt permeabilities range from P s = 1.3 × 10-16 m s-1 to 3.9 × 10-16 m s-1, and the estimated salt partition coefficients range from K s = 0.008 to 0.016. These measurements demonstrate that EIS is a powerful tool for studying membrane permselectivity through the measurement of salt permeability in thin polyamide films.

Tuning the Relaxation of Nanopatterned Polymer Films with Polymer-Grafted Nanoparticles: Observation of Entropy-Enthalpy Compensation.

Polymer films provide a versatile platform in which complex functional relief patterns can be thermally imprinted with a resolution down to few nanometers. However, a practical limitation of this method is the tendency for the imprinted patterns to relax ("slump"), leading to loss of pattern fidelity over time. While increasing temperature above glass transition temperature ( Tg) accelerates the slumping kinetics of neat films, we find that the addition of polymer-grafted nanoparticles (PGNP) can greatly enhance the thermal stability of these patterns. Specifically, increasing the concentration of poly(methyl methacrylate) (PMMA) grafted titanium dioxide (TiO2) nanoparticles in the composite films slows down film relaxation dynamics, leading to enhanced pattern stability for the temperature range that we investigated. Interestingly, slumping relaxation time is found to obey an entropy-enthalpy compensation (EEC) relationship with varying PGNP concentration, similar to recently observed relaxation of strain-induced wrinkling in glassy polymer films having variable film thickness. The compensation temperature,  Tcomp was found to be in the vicintity of the bulk  Tg of PMMA. Our results suggest a common origin of EEC relaxation in patterned polymer thin films and  nanocomposites.

Wrinkling-to-delamination transition in thin polymer films on compliant substrates.

Compressing a thin, stiff film attached to a thick, compliant substrate can lead to a number of different modes of mechanical deformation depending upon the material properties of the system. In this article we explore direct transitions from surface wrinkling to buckle delamination, and provide a theoretical framework for understanding the conditions under which such transitions take place, as well as the resulting dimensions of the wrinkling-induced delamination. A key conclusion of this work is that the width of the delamination blister formed from a wrinkled film is relatively strain-independent, suggesting that delaminations can be used in such systems to measure the adhesion energy at the film-substrate interface. In addition, we demonstrate how the length and width of delaminations can be tailored through straightforward control of the substrate and film properties in the system, illustrating how wrinkling delaminations can be used for both thin film metrology and patterning applications.

A wrinkling-based method for investigating glassy polymer film relaxation as a function of film thickness and temperature.

We investigate the relaxation dynamics of thin polymer films at temperatures below the bulk glass transition Tg by first compressing polystyrene films supported on a polydimethylsiloxane substrate to create wrinkling patterns and then observing the slow relaxation of the wrinkled films back to their final equilibrium flat state by small angle light scattering. As with recent relaxation measurements on thin glassy films reported by Fakhraai and co-workers, we find the relaxation time of our wrinkled films to be strongly dependent on film thickness below an onset thickness on the order of 100 nm. By varying the temperature between room temperature and Tg (≈100 °C), we find that the relaxation time follows an Arrhenius-type temperature dependence to a good approximation at all film thicknesses investigated, where both the activation energy and the relaxation time pre-factor depend appreciably on film thickness. The wrinkling relaxation curves tend to cross at a common temperature somewhat below Tg, indicating an entropy-enthalpy compensation relation between the activation free energy parameters. This compensation effect has also been observed recently in simulated supported polymer films in the high temperature Arrhenius relaxation regime rather than the glassy state. In addition, we find that the film stress relaxation function, as well as the height of the wrinkle ridges, follows a stretched exponential time dependence and the short-time effective Young's modulus derived from our modeling decreases sigmoidally with increasing temperature-both characteristic features of glassy materials. The relatively facile nature of the wrinkling-based measurements in comparison to other film relaxation measurements makes our method attractive for practical materials development, as well as fundamental studies of glass formation.

Ultraviolet/Ozone as a Tool To Control Grafting Density in Surface-Initiated Controlled-Radical Polymerizations via Ablation of Bromine.

We used an ultraviolet-ozone (UVO) cleaner to create substrates for atom-transfer radical polymerization (ATRP) with varying surface initiator coverage. We collected complementary time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS) measurements to investigate the precise chemical origin of the variation in grafting density. At short exposure times, the atomic composition underwent minor changes except for the relative amount of bromine. At longer UVO exposure times, there is clear evidence of exposure-dependent surface initiator oxidation. We interpret these data as evidence of a bromine ablation process within the UVO cleaner, with additional oxidative modification of the rest of the surface. We then used these substrates to create a series of poly(methyl methacrylate) (PMMA) brushes varying in grafting density, demonstrating the utility of this tool for the control of polymer brush density. The measured brush grafting densities were correlated with the bromine concentration measured by both ToF-SIMS and XPS. XPS and brush thicknesses correlated strongly, following an exponential decay with a half-life of 18 ± 1 s.

Confinement-driven increase in ionomer thin-film modulus.

Ion-conductive polymers, or ionomers, are critical materials for a wide range of electrochemical technologies. For optimizing the complex heterogeneous structures in which they occur, there is a need to elucidate the governing structure-property relationships, especially at nanoscale dimensions where interfacial interactions dominate the overall materials response due to confinement effects. It is widely acknowledged that polymer physical behavior can be drastically altered from the bulk when under confinement and the literature is replete with examples thereof. However, there is a deficit in the understanding of ionomers when confined to the nanoscale, although it is apparent from literature that confinement can influence ionomer properties. Herein we show that as one particular ionomer, Nafion, is confined to thin films, there is a drastic increase in the modulus over the bulk value, and we demonstrate that this stiffening can explain previously observed deviations in materials properties such as water transport and uptake upon confinement. Moreover, we provide insight into the underlying confinement-induced stiffening through the application of a simple theoretical framework based on self-consistent micromechanics. This framework can be applied to other polymer systems and assumes that as the polymer is confined the mechanical response becomes dominated by the modulus of individual polymer chains.

Tailoring the permselectivity of water desalination membranes via nanoparticle assembly.

Thin film composite membranes can selectively separate mono- and divalent ions from water via solution-diffusion of each species through a dense but ultrathin, highly cross-linked polymer "skin" layer; water is transported across the membrane faster than associated salts. Changing the selectivity of the "skin" layer typically requires adjusting the monomer chemistries that make up the polymer "skin" layer, but doing so also impacts a host of other membrane properties. Here, we employ electrostatic layer-by-layer deposition of inorganic nanoparticles to enhance the permselectivity of an existing commercial nanofiltration membrane. We chose this approach because it is simple and robust and does not require any change to the underlying chemistry of the thin film composite (TFC) membrane. We found that a single layer of nanoparticles was sufficient to increase the permselectivity of the membrane by nearly 50%, compared to the virgin TFC membrane. In order to understand the mechanism for permselectivity enhancement, we developed a modified solution-diffusion model to account for the additional hydraulic resistance of the nanoparticle layer, which can faithfully capture the effect of nanoparticle layer thickness on the observed water and salt flux of the modified TFC membrane.

Facile fabrication of "dual click" one- and two-dimensional orthogonal peptide concentration gradients.

Peptides, proteins, and extracellular matrix act synergistically to influence cellular function at the biotic-synthetic interface. However, identifying the individual and cooperative contributions of the various combinations and concentration regimes is extremely difficult. The confined channel deposition method we describe affords highly tunable orthogonal reactive concentration gradients that greatly expand the dynamic range, spatial control, and chemical versatility of the reactive silanes that can be controllably deposited. Using metal-free "dual click" immobilization chemistries, multiple peptides with a variety of functionality can be immobilized efficiently and reproducibly enabling optimal concentration profiling and the assessment of synergistic interactions.