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.

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.

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.

Enhanced resistance to decay of imprinted nanopatterns in thin films by bare nanoparticles compared to polymer-grafted nanoparticles.

We extend a previous study on the influence of nanoparticles on the decay of nanoimprinted polymer film patterns to compare the effects of "bare" silica (SiO2) nanoparticles and SiO2 nanoparticles with grafted polymer layers having the same chemical composition as the polymer matrix. This method involves nanoimprinting substrate-supported polymer films using a pattern replicated from a digital versatile disc (DVD), and then annealing the patterned polymer nanocomposite films at elevated temperatures to follow the decay of the topographic surface pattern with time by atomic force microscopy imaging after quenching. We quantified the relaxation of the pattern height ("slumping") and determined the relaxation time τ for this pattern decay process as a function of nanoparticle filler type and concentration to determine how nanoparticle additives influence relative film stability. Attractive interactions between the bare nanoparticles and the polymer matrix significantly enhance the thermal resilience of the nanopatterns to decay, compared to those of the particle brushes, wherein the particle core interactions are screened from the matrix via the brush layer. A novel aspect of this method is that it readily lends itself to in situ film relaxation measurements in a manufacturing context. We observe that the relaxation time of the pattern relaxation exhibits entropy-enthalpy compensation in the free energy parameters governing the pattern relaxation process as a function of temperature, irrespective of the NP system used, consistent with our previous experimental and computational studies.

Highly Permeable Reverse Osmosis Membranes via Molecular Layer-by-Layer Deposition of Trimesoyl Chloride and 3,5-Diaminobenzoic Acid.

We present a series of polyamide membranes synthesized via molecular layer-by-layer (mLbL) deposition of trimesoyl chloride (TMC) and 3,5-diaminobenzoic acid (BA). These membranes exhibit superior NaCl rejection compared to previously reported TMC-BA membranes prepared via interfacial polymerization, with the improved performance of the mLbL films attributable to higher cross-link density facilitated by the stepwise deposition process in good solvents. We compare the TMC-BA series with membranes synthesized from TMC and m-phenylenediamine (MPD), a conventional reverse osmosis membrane chemistry. At the minimum thickness capable of 90 % NaCl rejection, mLbL TMC-BA membranes exhibit 50 % greater water permeance than mLbL TMC-MPD.

Snakeskin-Inspired Elastomers with Extremely Low Coefficient of Friction under Dry Conditions.

Soft elastomers are critical to a broad range of existing and emerging technologies. One major limitation of soft elastomers is the large friction of coefficient (COF) due to inherently large adhesion and internal loss. In applications where lubrication is not applicable, such as soft robotics, wearable electronics, and biomedical devices, elastomers with inherently low dry COF are required. Inspired by the low COF of snakeskins atop soft bodies, this study reports the development of elastomers with low dry COF by growing a hybrid skin layer with a strong interface with a large stiffness gradient. Using a solid-liquid interfacial polymerization (SLIP) process, hybrid skin layers are imparted onto elastomers, which reduces the COF of the elastomers from 1.6 to 0.1, without sacrificing the bulk compliance and ductility of elastomer. Compared with existing surface modification methods, the SLIP process offers spatial control and ability to modify flat, prepatterned, curved, and inner surfaces, which is essential to engineer multifunctional skin layers for emerging applications.

Quantifying Strain via Buckling Instabilities in Surface Modified Polymer Brushes.

A compressive strain applied to bilayer films (e.g. thin film adhered to a thick substrate) can lead to buckled or wrinkled morphologies, which has many important applications in stretchable electronics, anti-counterfeit technology, and high-precision micro and nano-metrology. A number of buckling-based metrology methods have been developed to quantify the residual stress and viscoelastic properties of polymer thin films. However, in some systems (e.g. solvent-induced swelling or thermal strain), the compressive strain is unknown or difficult to measure. We present a quantitative method of measuring the compressive strain of wrinkled polymer films and coatings with knowledge of the "skin" thickness, wrinkle wavelength, and wrinkle amplitude. The derived analytical expression is validated with a well-studied model system, e.g., stiff, thin film (PS) bonded to a thick, compliant substrate (PDMS). After validation, we use our expression to quantify the applied swelling strain of previously reported wrinkled poly(styrene-alt-maleic anhydride) brush surfaces. Finally, the applied strain is used to rationalize the observed persistence length of aligned wrinkles created during atomic force microscopy (AFM) lithography and subsequent solvent exposure.

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.

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.

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.

Nanoscale Pattern Decay Monitored Line by Line via In Situ Heated Atomic Force Microscopy.

We combine in situ heated atomic force microscopy (AFM) with automated line-by-line spectral analysis to quantify the relaxation or decay phenomenon of nanopatterned composite polymer films above the glass-transition temperature of the composite material. This approach enables assessment of pattern fidelity with a temporal resolution of ≈1 s, providing the necessary data density to confidently capture the short-time relaxation processes inaccessible to conventional ex situ measurements. Specifically, we studied the thermal decay of nanopatterned poly(methyl methacrylate) (PMMA) and PMMA nanocomposite films containing unmodified and PMMA-grafted silica nanoparticles (SiO2 NP) of varying concentrations and film thicknesses using this new approach. Features imprinted on neat PMMA films were seen to relax at least an order of magnitude faster than the NP-filled films at decay temperatures above the glass transition of the PMMA matrix. It was also seen that patterned films with the lowest residual thickness (34 nm) filled with unmodified SiO2 NP decayed the slowest. The effect of nanoparticle additive was almost negligible in reinforcing the patterned features for films with the highest residual thickness (257 nm). Our in situ pattern decay measurement and the subsequent line-by-line spectral analysis enabled the investigation of various parameters affecting the pattern decay such as the underlying residual thickness, type of additive system, and temperature in a timely and efficient manner.

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 promise as next-generation NF membranes for desalination.

Role of the electronically-active amorphous state in low-temperature processed In2O3 thin-film transistors.

Metal oxide (MO) thin-film transistors (TFTs) are expected to enable low-cost flexible and printed electronics, given their excellent charge transport, low processing temperatures and solution processability. However, achieving adequate mobility when processed scalably at low temperatures compatible with plastic electronics is a challenge. Here, we explore process-structure-transport relationships in blade-coated indium oxide (In2O3) TFTs via both sol-gel and combustion chemistries. We find that the sol-gel chemistry enables n-type TFTs when annealed at 200 °C to 225 °C with noticeable electron mobility ((3.4 ± 1.3) cm2V-1s-1) yet minimal In2O3 crystallinity and surprisingly low levels of the metal-oxygen-metal (M-O-M) lattice content (≈46 %). Increased annealing temperatures result in the appearance of nanocrystalline domains and an increase in M-O-M content to ≈70 %, without any further increase in mobility. An actetylacetone combustion-assisted ink lowers the external thermal budget required for In2O3 crystallization but bypasses the electronically-active amorphous state and underperforms the sol-gel ink at low temperatures. Grain boundary formation and nanocrystalline inclusions in these films due to rapid combustion-assisted crystallization are suggested to be the likely origin behind the significantly compromised charge transport at low-temperatures. Overall, this study emphasizes the need to understand the complex interplay between local order (nanocrystallinity) and connectivity (grain boundary, amorphous phases) when optimizing low-temperature processed MO thin films.

Unexpectedly Strong Size-Sieving Ability in Carbonized Polybenzimidazole for Membrane H2/CO2 Separation.

Polymers with high permeability and strong size-sieving ability are needed for H2/CO2 separation at temperatures ranging from 100 to 300 °C to enable an energy-efficient precombustion CO2 capture process. However, such polymers usually suffer from a permeability/selectivity tradeoff, that is, polymers with high permeability tend to exhibit a weak size-sieving ability and thus low selectivity. Herein, we demonstrate that carbonization of a suitable polymer precursor (i.e., polybenzimidazole or PBI) generates microcavities (leading to high H2 permeability) and ultramicroporous channels (leading to strong size-sieving ability and thus high H2/CO2 selectivity). Specifically, carbonization of PBI at 900 °C (CMS@900) doubles H2 permeability and increases H2/CO2 selectivity from 14 to 80 at 150 °C. When tested with simulated syngas-containing equimolar H2 and CO2 in the presence of water vapor for 120 h, CMS@900 exhibits stable H2 permeability of ≈36 barrer and H2/CO2 selectivity of ≈53 at 150 °C, above Robeson's 2008 upper bound and demonstrating robustness against physical aging and CO2 plasticization.

A general approach to multicomponent metal-decorated crumpled reduced graphene oxide nanocomposites using a flame-based process.

We introduce a general approach for synthesizing multicomponent metal-decorated crumpled reduced graphene oxide nanocomposites using a one-step, continuous flame-based process. Crumpled reduced graphene oxide balls (CGB) were produced from graphene oxide (GO) in a High Temperature Reducing Jet (HTRJ) reactor. Moreover, CGBs were simultaneously decorated with different transition metal nanoparticles, including cobalt (Co), nickel (Ni), iron (Fe), and palladium (Pd). Various metal alloy-decorated crumpled reduced graphene oxide balls (M-CGBs) including CoPd-, CoNi-, CoPdNi-, and CoNiFe-CGBs were successfully synthesized using a general recipe. The key advantage of the HTRJ system over common flame-based aerosol synthesis methods is the separation of flame and product formation zones, which allows production and/or reduction of nanomaterials that can be reduced by H2 in the presence of H2O. Nanomaterials are produced from aqueous precursors containing low-cost metal salts and dispersed GO. Electron microscopy and other characterization methods show the decoration of the CGBs with sub-4 nm diameter binary and ternary alloy, non-oxide transition metal nanoparticles of controlled compositions. The nanostructures made by this process can potentially be used as electrocatalysts for fuel cells, electrodes in batteries and supercapacitors, conductive inks for printed electronics, catalysts in wastewater treatment, and many other applications where a graphitized carbon-metal nanomaterial is needed.

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.

Controlled Growth of Polyamide Films atop Homogenous and Heterogeneous Hydrogels using Gel-Liquid Interfacial Polymerization.

Controlled growth of crosslinked polyamide (PA) thin films is demonstrated at the interface of a monomer-soaked hydrogel and an organic solution of the complementary monomer. Termed gel-liquid interfacial polymerization (GLIP), the resulting PA films are measured to be chemically and mechanically analogous to the active layer in thin film composite membranes. PA thin films are prepared using the GLIP process on both a morphologically homogeneous hydrogel prepared from poly(2-hydroxyethylmethacrylate) (PHEMA) and a phase-separated, heterogeneous hydrogel prepared from poly(acrylamide) (PAAm). Two monomer systems are examined: trimesoyl chloride (TMC) reacting with m-phenylene diamine (MPD) and TMC reacting with piperazine (PIP). Unlike the self-limiting growth behavior in TFC membrane fabrication, diffusion-limited, continuous growth of the PA films is observed, where both the thickness and roughness of the PA layers increase with reaction time. A key morphological difference is found between the two monomer systems using the GLIP process: TMC/MPD produces a ridge-and-valley surface morphology whereas TMC/PIP produces nodule/granular structures. The GLIP process represents a unique opportunity to not only explore the pore characteristics (size, spacing, and continuity) on the resulting structure and morphology of interfacially polymerized thin films, but also a method to modify the surface of (or encapsulate) hydrogels.