Grazing Incidence Small Angle Research Articles

From adsorption to crystallization of proteins: Evidence for interface-assisted nucleation

Protein crystallization is among the key processes in biomolecular research, but the underlying mechanisms are still elusive. Here, we address the role of inevitable interfaces for the nucleation process. Quartz crystal microbalance with dissipation monitoring (QCM-D) with simultaneously optical microscopy, confocal microscopy, and grazing-incidence small angle X-rays scattering (GISAXS) were employed to investigate the temporal behavior from the initial stage of protein adsorption to crystallization. Here we studied the crystallization of the Human Serum Albumin (HSA), the most abundant blood protein, in the presence of a charged surface and a trivalent salt. We found evidence for interface-assisted nucleation of crystals. The kinetic stages involved are initial adsorption followed by enhanced adsorption after longer times, subsequent nucleation, and finally crystal growth. The results highlight the importance of interfaces for protein phase behavior and in particular for nucleation.

Morphology of Buried Interfaces in Ion-Assisted Magnetron Sputter-Deposited 11B4C-Containing Ni/Ti Multilayer Neutron Optics Investigated by Grazing-Incidence Small-Angle Scattering.

Multilayer neutron optics require precise control of interface morphology for optimal performance. In this work, we investigate the effects of different growth conditions on the interface morphology of Ni/Ti-based multilayers, with a focus on incorporating low-neutron-absorbing 11B4C and using different ion assistance schemes. Grazing-incidence small-angle X-ray scattering was used to probe the structural and morphological details of buried interfaces, revealing that the layers become more strongly correlated and the interfaces form mounds with increasing amounts of 11B4C. Applying high flux ion assistance during growth can reduce mound formation but lead to interface mixing, while a high flux modulated ion assistance scheme with an initial buffer layer grown at low ion energy and the top layer at higher ion energy prevents intermixing. The optimal condition was found to be adding 26.0 atom % 11B4C combined with high flux modulated ion assistance. A multilayer with a period of 48.2 Å and 100 periods was grown under these conditions, and coupled fitting to neutron and X-ray reflectivity data revealed an average interface width of only 2.7 Å, a significant improvement over the current state-of-the-art commercial Ni/Ti multilayers. Overall, our study demonstrates that the addition of 11B4C and the use of high flux modulated ion assistance during growth can significantly improve the interface morphology of Ni/Ti multilayers, leading to improved neutron optics performance.

Highly Ordered Monolayers of μm-Sized Polystyrene Spheres Studied by Grazing-Incidence Small-Angle X-ray Scattering, Simulations, and Geometrical Calculations.

Unraveling the two-dimensional (2D) structural ordering of colloidal particles assembled at a flat surface is essential for understanding and optimizing their physical properties. So far, grazing-incidence small-angle X-ray scattering (GISAXS) has been widely used to determine crystallographic information on 2D self-assembled structures of nanosize objects. However, solving the structure of 2D lattices consisting of micrometer (μm)-sized objects still remains a challenge using scattering methods. Here, a model 2D SCALMS (supported catalytically active liquid metal solution) template is fabricated from μm-sized polystyrene (PS) spheres that form a monolayer on top of the flat solid support. GISAXS patterns of the sample were collected for rotation angles around its surface normal in steps of 3°. For every rotation angle, different Bragg-type interference maxima along the out-of-plane (qz) direction were observed. On the basis of simulations of GISXAS patterns of single domains of ordered particle arrangements using the distorted wave Born approximation (DWBA) and validation against a simple geometrical scattering model, the interference maxima could nicely be interpreted to originate from a monolayer of the μm-sized spherical particles which are arranged in domains of hexagonal 2D paracrystalline order. This novel GISAXS evaluation technique serves as a proof of principle for determining the μm-size periodicity of 2D crystalline domains and demonstrates its potential to spatially resolve the relative orientations of such domains with respect to a reference direction.

Measurement of Two-Dimensional Orthogonal Gratings Using Grazing-Incidence Small-Angle X-Ray Scattering

Measurement of Two-Dimensional Orthogonal Gratings Using Grazing-Incidence Small-Angle X-Ray Scattering

News Article

Book, “X-Ray Spectroscopy for Chemical State Analysis” (Jun Kawai, Springer, 2023) Professor Jun Kawai (Kyoto University, Japan) has published an interesting and useful book on materials characterization methods using X-ray emission, absorption, and photoelectron spectroscopies. Readers will be able to learn about basic X-ray physics topics such as “Particle and Wave Duality of X-rays” (Chapter 1), “Profile Change of X-Ray Spectra” (Chapter 2), and “Chemical Effects of Multiply Ionized Satellites” (Chapter 3). They can also gain some practical knowledge on instrumentation, including “Pyroelectric X-Ray Emission” (Chapter 4), “Small-Size and Low-Power X-Ray Instruments” (Chapter 5), “Synchrotron Radiation Experiments” (Chapter 6), and “Quantitative Analysis Using XRF and SEM” (Chapter 7). The book includes some interesting historical episodes, such as Professor Yoneda's discovery of enhanced diffuse scattering at the total reflection critical angle (now often called the Yoneda peak or Yoneda wing in grazing-incidence small angle X-ray scattering) and TXRF. The author also describes his own experience - how he has achieved novel experiments. The book consists of 243 pages. Overall, this book seems to provide a good overview of X-ray spectroscopy methods and their applications. The inclusion of historical context and the author's experiences helps to give readers insight into how these techniques were developed and applied in practice. For further information of the book, see the following page, https://doi.org/10.1007/978-981-19-7361-1

Grazing-incidence small angle neutron scattering achieved in spectrometer SANS-Suanni of transmission geometry

Current work presents the design and applications of the grazing-incidence small-angle neutron scattering (GISANS) based on SANS-Suanni spectrometer at the 20 MW China Mianyang research reactor (CMRR)-based neutron center. A multi-dimensional sample stage with both front and back slits were designed and set up on SANS-Suanni for achieving the geometry. Experimentally, thin films samples with mono-dispersed silica on sapphire substrates were prepared for collecting two-dimensional (2D) GISANS patterns at beam size setting of 4 mm width and 5 mm height. Typical signals such as the specular reflection peak, Yoneda peak, as well as the sample scattering, etc. were obtained. Moreover, integrated 1D GISANS profiles in different directions, namely vertical and horizontal directions of the incident beam (0V, 0H), and horizontal direction of the Yoneda peak (YH) were obtained via rectangular integration. Accordingly, incident angle (αi) as about 0.76° and the contrast of the sample systems as around 4.07 × 1010 cm−2 were determined. Moreover, the overlapping of 0H curves and the SANS profiles indicates that GISANS can cover some of the structural information as SANS provided, along with the capability of measuring the thin film samples.

Cluster-layered [Fe/Cr]30 structure exhibited Kondo-like effect studied by GISAXS and Mössbauer spectroscopy

Structure and morphology of epitaxial [Fe/Cr]30 multilayers with ultrathin Fe layers (nominally 0.12 nm and 0.08 nm) have been investigated by X-ray reflectivity, synchrotron Mössbauer spectroscopy at low temperature and grazing-incidence small angle X-ray scattering (GISAXS). The films demonstrate Kondo-like behavior of electrical resistivity. The GISAXS patterns reveal their cluster-layered structure. The observed side maxima give the information about the sizes and distances between lateral inhomogeneities. Mössbauer reflectivity spectra measured below the critical angle of the total reflection support the existence of the cluster-layered structure of the samples. Magnetic hyperfine field distributions show that largest number of 57Fe atoms is situated in interfaces of iron clusters and their number increases in the thinnest films.

(Invited) Structure-Property Relationships in Highly Permeable Dioxolane-Based Perfluorinated Ionomers

Ion conducting polymers used as membranes and catalyst binders in membrane electrode assemblies (MEAs) have driven continuous improvements in fuel cell performance. Commercially available membrane materials (e.g., Nafion®) impart low gas permeability, high chemical and mechanical stability thanks to their semi-crystalline polytetrafluoroethylene (PTFE) matrix. This dense matrix also slows permeation of gases through the polymer, introducing significant mass-transport losses in the catalyst layers and limits fuel cell performance. In this presentation, I will discuss a new family of perfluorinated ionomers that incorporates an amorphous matrix based on a perfluoro(2-methylene 4-methyl-1,3-dioxolane) (PFMMD) backbone. The introduction of a PFMMD backbone disrupts the crystallinity of the matrix, increases the matrix free volume, and significantly improves its gas permeability.1 The dioxolane backbone also increases the glass transition temperature of the matrix, impacting its mobility, limiting the ionomer domain swelling and reducing its proton conductivity. I will describe a flexible synthesis method for PFMMD-based ionomers which allowed us to study ionomers with tunable sulfonic acid content and derive structure-property relationships through a combination of transport measurements (i.e., water uptake, proton conductivity, and permeability) and morphological characterization through Small- and Wide-angle X-ray scattering. We will show how the incorporation of dioxolane monomers with bulky, asymmetric side-chains results in a stiff ionomer matrix with distinct chemical and mechanical properties. By varying the dioxolane matrix mass fraction, we gained fundamental insights into the role of the matrix chemical structure on the dynamics of structural and transport processes in ion-conducting polymers.2 Through in situ water uptake measurements, we elucidated the impact of the mass fraction and matrix chemical structure on water sorption rates. The mass-transport swelling rate of Nafion was around 50% higher than in dioxolane-containing ionomers and was independent of the matrix mass fraction. Non-Fickian polymer relaxation rate was sensitive to both type and fraction of the matrix, increasing by 22% across the range of dioxolane fractions studied and by another 100% in Nafion. These effects are attributed to reduction of segmental mobility of the hydrophobic matrix upon incorporation of dioxolane groups. The polymer relaxation is shown to correlate to changes in ionomer conductivity and nanostructure, reveled through in situ Grazing-Incidence Small Angle X-ray Scattering (GISAXS) measurements, showing two distinct physical processes that enable (i) rapid water sorption and ionomer domain swelling and (ii) polymer relaxation and ordering of ionomer domain structure. Lastly, I will discuss the implication and potential utilization of these new materials for improved fuel cell performance. The results presented here underscore the significance of tailoring materials chemistry to specific requirements of fuel cell or electrolysis MEAs.

Strong Induced Circular Dichroism in a Hybrid Lead‐Halide Semiconductor Using Chiral Amino Acids for Crystallite Surface Functionalization

AbstractChirality is a desired property in functional semiconductors for optoelectronic, catalytic, and spintronic applications. Here, introducing enantiomerically‐pure 3‐aminobutyric acid (3‐ABA) into thin films of the 1D semiconductor dimethylammonium lead iodide (DMAPbI3) is found to result in strong circular dichroism (CD) in the optical absorption. X‐ray diffraction and grazing incidence small angle X‐ray scattering (GISAXS) are applied to gain molecular‐scale insights into the chirality transfer mechanism, which is attributed to a chiral surface modification of DMAPbI3 crystallites. This study demonstrates that the CD signal strength can be controlled by the amino‐acid content relative to the crystallite surface area. The CD intensity is tuned by the composition of the precursor solution and the spin‐coating time, thereby achieving anisotropy factors (gabs) as high as 1.75 × 10–2. Grazing incidence wide angle scattering reveals strong preferential ordering that can be suppressed via tailored synthesis conditions. Different contributions to the chiroptical properties are resolved by a detailed analysis of the CD signal utilizing an approach based on the Mueller matrix model. This report of a novel class of chiral hybrid semiconductors with precise control over their optical activity presents a promising approach for the design of circularly polarized light detectors and emitters.

APIE: an angle calibration algorithm for reflection ptychography.

Reflection ptychography is a lensfree microscopy technique particularly promising in regions of the electromagnetic spectrum where imaging optics are inefficient or not available. This is the case in tabletop extreme ultraviolet microscopy and grazing incidence small angle x ray scattering experiments. Combining such experimental configurations with ptychography requires accurate knowledge of the relative tilt between the sample and the detector in non-coplanar scattering geometries. Here, we describe an algorithm for tilt estimation in reflection ptychography. The method is verified experimentally, enabling sample tilt determination within a fraction of a degree. Furthermore, the angle-estimation uncertainty and reconstruction quality are studied for both smooth and highly structured beams.

In Situ Study of Nanoporosity Evolution during Dealloying AgAu and CoPd by Grazing-Incidence Small-Angle X-ray Scattering.

Electrochemical dealloying has become a standard technique to produce nanoporous network structures of various noble metals, exploiting the selective dissolution of one component from an alloy. While achieving nanoporosity during dealloying has been intensively studied for the prime example of nanoporous Au from a AgAu alloy, dealloying from other noble-metal alloys has been rarely investigated in the scientific literature. Here, we study the evolution of nanoporosity in the electrochemical dealloying process for both CoPd and AgAu alloys using a combination of in situ grazing-incidence small-angle X-ray scattering (GISAXS), kinetic Monte Carlo (KMC) simulations, and scanning transmission electron microscopy (STEM). When comparing dealloying kinetics, we find a more rapid progression of the dealloying front for CoPd and also a considerably slower coarsening of the nanoporous structure for Pd in relation to Au. We argue that our findings are natural consequences of the effectively higher dealloying potential and the higher interatomic binding energy for the CoPd alloy. Our results corroborate the understanding of electrochemical dealloying on the basis of two rate equations for dissolution and surface diffusion and suggest the general applicability of this dealloying mechanism to binary alloys. The present study contributes to the future tailoring of structural size in nanoporous metals for improved chemical surface activity.

Highly oriented NiSi2@Si thin-nanocomposite produced by solid state diffusion: Morphological and crystallographic characterization

This article describes a morphological and crystallographic multi-technique characterization of a 2D-nanocomposite consisting of highly oriented NiSi2 nanoplates endotaxially grown inside a single-crystalline Si(001) wafer close to its external surface. This nanostructured material is prepared using a novel procedure which promotes the diffusion of Ni atoms from a deposited Ni-dopped-SiO2 thin film into the volume of a Si(001) flat wafer under controlled thermodynamic conditions. High Resolution Scanning Transmission Electron Microscopy images reveal the formations of well oriented thin hexagonal nanoplates totally buried inside a Si(001) wafer and randomly oriented nearly spherical Ni nanocrystals located inside the Ni-doped SiO2 thin film and also inside a thin layer close to external surface of the Si(001) wafer. The NiSi2 nanoplates formed by endotaxial growth have their large hexagonal flat surfaces parallel to one of the four Si{111} crystallographic planes and exhibit coherent 7A-type interfaces with the host Si matrix. Additional analyses of Grazing-Incidence Small-Angle X-ray Scattering patterns - which probe a high number of nanoparticles - indicated that the average thickness and maximum diameter of NiSi2 nanoplates are 12 nm and 118 nm, respectively, and the average radius of Ni nanocrystals is 1.7 nm. The described process for obtaining 2D-NiSi2@Si nanocomposites opens new possibilities for exploiting the structural features of these materials for use in devices requiring anisotropic electrical transport properties.

Alignment frustration in block copolymer films with block copolymer grafted TiO2 nanoparticles under soft‐shear cold zone annealing

AbstractBlock copolymers (BCPs) have received significant attention as promising candidates for sequestering nanoparticles and fabrication of aligned nanostructures with optimal optical or electrical properties. We investigate the influence of static and dynamic thermal field on the alignment of polystyrene‐block‐poly(methyl methacrylate) (PS‐b‐PMMA) BCP morphology with the loading of novel poly(methyl methacrylate‐block‐Polystyrene) (PMMA‐b‐PS)‐grafted‐TiO2 nanoparticles (BCP‐g‐TiO2). Observation of characteristics IR peaks for PMMA and PS in BCP‐g‐TiO2 nanoparticles and Transmission Electron Microscopy (TEM) results of the outer coating of core nanoparticle, validate the grafting to approach in synthesizing BCP‐g‐TiO2. Here we report that under the sharp dynamic thermal field, at low loading of BCP‐g‐TiO2, there is good dispersion of nanoparticles in unidirectionally aligned BCP matrix in film interior probed by GISAXS, while, at high nanoparticle loading (~10 wt%), there is local frustration in the unidirectional alignment of the BCP matrix due to aggregation of BCP‐g‐TiO2 nanoparticles. However, Grazing incidence small angle X‐ray scattering (GISAXS) shows clearly that the BCP films remain largely locally ordered at the domain scale, despite these large perturbations to long‐range ordering even at high loading level, while bringing in new TiO2 functionality to the BCP films, such as UVO absorptivity or biofouling prevention, important to potential new applications of such membranes.

Light‐Induced and Oxygen‐Mediated Degradation Processes in Photoactive Layers Based on PTB7‐Th

Low‐bandgap polymers are sensitive to various degradation processes, which strongly decrease their lifetime. The chemical and physical changes occurring in the low‐bandgap polymer with benzodithiophene units poly[4,8‐bis(5‐(2‐ethylhexyl)thiophene‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl‐alt‐(4‐(2‐ethylhexyl)‐3‐fluorothieno[3,4‐b]thiophene‐2‐carboxylate] (PTB7‐Th) and its blend with the fullerene derivative [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC71BM) are followed during irradiation‐induced aging by combination of various characterization methods. The active layer morphology is investigated using atomic force microscopy (AFM) as well as in‐operando grazing incidence small angle X‐ray scattering (GISAXS), indicating morphological alterations and material loss due to chemical modifications. Optical spectroscopy gives insights into these chemical processes which lead to significant absorption losses under ambient conditions. Independent of the energy of the absorbed photons, but only in combination with oxygen, the excitation of the polymer leads to a fatal increase in oxidation probability. Fourier transform infrared (FTIR) data highlight the sensitivity of the conjugated polymer backbone to oxidation, a result of lost conjugation and therefore absorption capability. With combined AFM height and infrared (IR) mapping, the chemical degradation and material loss is confirmed on a nanoscale. Although the chemical structure is seriously damaged, the blend morphology is not undergoing major changes.

Following in Operando the Structure Evolution‐Induced Degradation in Printed Organic Solar Cells with Nonfullerene Small Molecule Acceptor

Understanding the degradation mechanisms of printed bulk‐heterojunction (BHJ) organic solar cells during operation is essential to achieve long‐term stability and realize real‐world applications of organic photovoltaics. Herein, the degradation of printed organic solar cells based on the conjugated benzodithiophene polymer PBDB‐T‐SF and the nonfullerene small molecule acceptor IT‐4F with 0.25 vol% 1,8‐diiodooctane (DIO) solvent additive is studied in operando for two different donor:acceptor ratios. The inner nano‐morphology is analyzed with grazing incidence small angle X‐ray scattering (GISAXS), and current–voltage (I–V) characteristics are probed simultaneously. Irrespective of the mixing ratio, degradation occurs by the same degradation mechanism. A decrease in the short‐circuit current density (JSC) is identified to be the determining factor for the decline of the power conversion efficiency. The decrease in JSC is induced by a reduction of the relative interface area between the conjugated polymer and the small molecule acceptor in the BHJ structure, resembling the morphological degradation of the active layer.

In Situ Printing: Insights into the Morphology Formation and Optical Property Evolution of Slot‐Die‐Coated Active Layers Containing Low Bandgap Polymer Donor and Nonfullerene Small Molecule Acceptor

Printing of active layers for high‐efficiency organic solar cells with the slot‐die coating technique can overcome the challenge of upscaling, which will be needed for organic photovoltaics on its way to marketability. The morphology of a bulk‐heterojunction organic solar cell has a very high impact on its power conversion efficiency. Therefore, it is of particular importance to understand the mechanisms of structure formation during printing of active layers to enable further optimization of the solar cell performance and upscaling of the production process. Meniscus‐guided slot‐die coating of the blend of a low bandgap conjugated polymer donor with benzodithiophene units PBDB‐T‐SF and the nonfullerene small molecule acceptor IT‐4F is studied in situ with optical microscopy, Ultraviolet–visible spectroscopy, and grazing incidence small angle X‐ray scattering. The structure formation is followed from the liquid to the final dry film state. Thereby, five regimes of morphology formation are determined. The morphological evolution in the printed active layer is correlated to changing optical properties of the thin film. In the final dry film, polymer domains of several tens of nanometers are observed, which will be favorable for application in high‐efficiency organic solar cells.

Key Factors for Template‐Oriented Porous Titania Synthesis: Solvents and Catalysts

AbstractVarious types of titania nanostructures are synthesized with a polymer‐templated sol–gel method based on the amphiphilic diblock copolymer polystyrene‐b‐polyethylene oxide (PS‐b‐PEO) in combination with selective incorporation of the titania precursor titanium tetraisopropoxide. Custom tailoring of different types of titania morphologies is realized by changing the phase separation behavior of the PS‐b‐PEO template. Particularly, application of solvents from different categories is found to have a major impact upon the phase separation behavior of PS‐b‐PEO and the final titania film morphology. The amount of available hydrochloric acid catalyst during the gelation process is seen as an additional key factor to induce controllable morphological changes. Scanning electron microscopy and grazing incidence small angle X‐ray scattering measurements are carried out to study the surface and inner structure of porous titania films. Systematic analysis and comparison of different characterization results allow attributing the following three factors to the respectively formed titania nanostructure: the surface energy between PS blocks and surrounding solvent, the aggregation behavior of the titania nanoparticles, and the block‐specific selectivity of the used solvent. For all synthesized titania thin films, an anatase‐type crystallization is confirmed through X‐ray powder diffraction.

Grazing-Incidence Small-Angle X-Ray Scattering (GISAXS) and Grazing-Incidence Wide-Angle X-Ray Scattering (GIWAXS) Comparative Study on Malignant and Benign Human Cancer Cells and Tissues under Synchrotron Radiation

In the current study, we have experimentally and comparatively investigated and compared malignant human cancer cells and tissues before and after irradiating of synchrotron radiation using Grazing-Incidence Small-Angle X-Ray Scattering (GISAXS) and Grazing-Incidence Wide-Angle X-Ray Scattering (GIWAXS). It is clear that malignant human cancer cells and tissues have gradually transformed to benign human cancer cells and tissues under synchrotron radiation with the passing of time.

Quantification of porosity in extensively nanoporous thin films in contact with gases and liquids

Nanoporous layers are widely spread in nature and among artificial devices. However, complex characterization of extensively nanoporous thin films showing porosity-dependent softening lacks consistency and reliability when using different analytical techniques. We introduce herein, a facile and precise method of such complex characterization by multi-harmonic QCM-D (Quartz Crystal Microbalance with Dissipation Monitoring) measurements performed both in the air and liquids (Au-Zn alloy was used as a typical example). The porosity values determined by QCM-D in air and different liquids are entirely consistent with that obtained from parallel RBS (Rutherford Backscattering Spectroscopy) and GISAXS (Grazing-Incidence Small-Angle Scattering) characterizations. This ensures precise quantification of the nanolayer porosity simultaneously with tracking their viscoelastic properties in liquids, significantly increasing sensitivity of the viscoelastic detection (viscoelastic contrast principle). Our approach is in high demand for quantifying potential-induced changes in nanoporous layers of complex architectures fabricated for various electrocatalytic energy storage and analytical devices.

Utilizing a Tunable Triblock Copolymer for Design of Model Systems to Study Interactions at the Anion Exchange Polymer-Catalyst Interface

The heterogeneous microstructure of the electrode in polymer electrolyte-based electrochemical devices is not well understood. Due to its complex nature, it is challenging to investigate in a meaningful way. Model systems need to be designed to study controlled interfaces between polymer electrolytes and catalyst particles or surfaces. It is known from studies on proton exchange membranes that restructuring can occur at the polymer-catalyst interface and propagate into the bulk morphology of the material. This is potentially to the detriment of reactant and product species transport in the electrode, and ultimately affects device performance. There is currently little to no work reported on interactions between anion exchange polymers and non-precious metal catalysts more relevant to alkaline systems, such as silver or nickel. This research utilizes a highly tunable ABA triblock copolymer (polychloromethylstyrene-b-polycyclooctene-b-polychloromethylstyrene) to investigate different parameters within the chemistry space and how they influence interactions between the polymer and a catalyst surface. The synthesis route for the triblock copolymer has been optimized to achieve a variety of block lengths and A:B ratios, which ultimately lead to a range of characteristics (ionic conductivity, water uptake, mechanical properties) and morphologies when they are post-quaternized to produce AEMs. Additionally, the polycyclooctene (PCOE) midblock contains C=C double bonds that allow for a variety of post-modifications, such as radical crosslinking and hydrogenation. This system has given us a way to make changes to the chemistry and morphology of the polymer and investigate the effect on interactions at a silver surface. The polymer-catalyst interface has been fabricated for study in two different model systems – as a thin film on a flat surface of silver and in a constrained environment of silver nanoparticles. The structure and properties of the anion exchange polymer in these systems will be representative of any changes that occur due to interactions with the catalyst. In the thin film geometry, the properties of the polymer are studied by comparing the ‘bulk’ properties (represented as a thin film on atomically flat silicon where there are no interactions) with those of a thin film on a silver surface. Samples of varying thickness and chemistry have been prepared and the morphology of each system has been investigated using grazing incidence small angle and wide angle x-ray scattering (GISWAXS) and atomic force microscopy (AFM). Clear differences were found between the bulk properties and those at the silver interface that indicate a strong interaction between the anion exchange polymer and a silver catalyst surface. These change as a function of the various parameters under investigation, including A:B block ratios, molecular weight, chemistry of the polymer backbone, and chemistry of the quaternary ammonia cation group. For AEMs in silver nanoparticle constrained environments, properties under investigation are compared to those of the bulk polymer. Areas of current work include studying changes in thermal characteristics (using thermogravimetric analysis and differential scanning calorimetry), morphology (using transmission electron spectroscopy and small angle x-ray scattering), backbone crystallinity (using wide angle x-ray scattering), ionic and electrical conductivity, alkaline stability, vapor and liquid water uptake, and mechanical properties. Interactions between specific chemical groups are also being investigated with Fourier-transform infrared spectroscopy (FTIR). Furthering the understanding of interactions and morphological changes at the polymer-catalyst interfaces will provide a framework for rational design of anion exchange polymers. Ultimately, improvements in polymer design can have significant impacts on the transport of species in the electrode layer and overall device performance.