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An important and integral effort toward understanding the formation and reorganization of mesoscale structures in functional organic thin films, being of fundamental importance to the development o...

Experimental nondestructive methods for probing the spatially varying arrangement and orientation of ultrastructures in hierarchical materials are in high demand. While conventional computed tomography (CT) is the method of choice for nondestructively imaging the interior of objects in three dimensions, it retrieves only scalar density fields. In addition to the traditional absorption contrast, other contrast mechanisms for image formation based on scattering and refraction are increasingly used in combination with CT methods, improving both the spatial resolution and the ability to distinguish materials of similar density. Being able to obtain vectorial information, like local growth directions and crystallite orientations, in addition to scalar density fields, is a longstanding scientific desire. In this work, it is demonstrated that, under certain conditions, the spatially varying preferred orientation of anisotropic particles embedded in a homogeneous matrix can be retrieved using CT with small-angle X-ray scattering as the contrast mechanism. Specifically, orientation maps of filler talc particles in injection-moulded isotactic polypropylene are obtained nondestructively under the key assumptions that the preferred orientation varies slowly in space and that the orientation of the flake-shaped talc particles is confined to a plane. It is expected that the method will find application inin situstudies of the mechanical deformation of composites and other materials with hierarchical structures over a range of length scales.

International audience; Characterization of the wavefront of an X-ray beam is of primary importance for all applications where coherence plays a major role. Imaging techniques based on numerically retrieving the phase from interference patterns are often relying on an a-priori assumption of the wavefront shape. In Coherent X-ray Diffraction Imaging (CXDI) a planar incoming wave field is often assumed for the inversion of the measured diffraction pattern, which allows retrieving the real space image via simple Fourier transformation. It is therefore important to know how reliable the plane wave approximation is to describe the real wavefront. Here, we demonstrate that the quantitative wavefront shape and flux distribution of an X-ray beam used for CXDI can be measured by using a micrometer size metal-coated polymer sphere serving in a similar way as the hole array in a Hartmann wavefront sensor. The method relies on monitoring the shape and center of the scattered intensity distribution in the far field using a 2D area detector while raster-scanning the microsphere with respect to the incoming beam. The reconstructed X-ray wavefront was found to have a well-defined central region of approximately 16 mu m diameter and a weaker, asymmetric, intensity distribution extending 30 mu m from the beam center. The phase front distortion was primarily spherical with an effective radius of 0.55 m which matches the distance to the last upstream beam-defining slit, and could be accurately represented by Zernike polynomials. (C) 2016 Optical Society of America

Coherent x-ray diffraction imaging (CXDI) is becoming an important 3D quantitative microscopy technique, allowing structural investigation of a wide range of delicate mesoscale samples that cannot be imaged by other techniques like electron microscopy. Here we report high-resolution 3D CXDI performed on spherical microcomposites consisting of a polymer core coated with a triple layer of nickel–gold–silica. These composites are of high interest to the microelectronics industry, where they are applied in conducting adhesives as fine-pitch electrical contacts—which requires an exceptional degree of uniformity and reproducibility. Experimental techniques that can assess the state of the composites non-destructively, preferably also while embedded in electronic chips, are thus in high demand. We demonstrate that using CXDI, all four different material components of the composite could be identified, with radii matching well to the nominal specifications of the manufacturer. Moreover, CXDI provided detailed maps of layer thicknesses, roughnesses, and defects such as holes, thus also facilitating cross-layer correlations. The side length of the voxels in the reconstruction, given by the experimental geometry, was 16 nm. The effective resolution enabled resolving even the thinnest coating layer of ∼20 nm nominal width. We discuss critically the influence of the weak phase approximation and the projection approximation on the reconstructed electron density estimates, demonstrating that the latter has to be employed. We conclude that CXDI has excellent potential as a metrology tool for microscale composites.

Phase-contrast three-dimensional tomograms showing in unprecedented detail the mechanical response of a micro-composite subjected to a mechanical compression test are reported. The X-ray ptychography images reveal the deformation and fracture processes of a 10 μm diameter composite, consisting of a spherical polymer bead coated with a nominally 210 nm metal shell. The beginning delamination of the shell from the core can be directly observed at an engineering strain of a few percent. Pre-existing defects are shown to dictate the deformation behavior of both core and shell. The strain state of the increasingly compressed polymer core is assessed quantitatively through the local densification at sub-micron resolution, supported by finite element analysis. Nanoscale mechanics is of rapidly growing importance in materials science, biotechnology and medicine, and this study demonstrates the use of coherent X-ray microscopy as a powerful tool for in situ studies of the mechanical properties of nanostructured devices, structures, and composites.

Organic solar cells have great potential for upscaling due to roll-to-roll processing and a low energy payback time, making them an attractive sustainable energy source for the future. Active layers coated with water-dispersible Landfester particles enable greater control of the layer formation and easier access to the printing industry, which has reduced the use of organic solvents since the 1980s. Through ptychographic X-ray computed tomography (PXCT), we image quantitatively a roll-to-roll coated photovoltaic tandem stack consisting of one bulk heterojunction active layer and one Landfester particle active layer. We extract the layered morphology with structural and density information including the porosity present in the various layers and the silver electrode with high resolution in 3D. The Landfester particle layer is found to have an undesired morphology with negatively correlated top- and bottom interfaces, wide thickness distribution and only partial surface coverage causing electric short circuits through the layer. By top coating a polymer material onto the Landfester nanoparticles we eliminate the structural defects of the layer such as porosity and roughness, and achieve the increased performance larger than 1 V expected for a tandem cell. This study highlights that quantitative imaging of weakly scattering stacked layers of organic materials has become feasible by PXCT, and that this information cannot be obtained by other methods. In the present study, this technique specifically reveals the need to improve the coatability and layer formation of Landfester nanoparticles, thus allowing improved solar cells to be produced.

A major limitation to the use of coherent X-ray diffraction imaging (CXDI) for imaging soft materials like polymers and biological tissue is that the radiation can cause extensive damage to the sample under investigation. In this study, CXDI has been used to monitor radiation-induced structural changes in metal-coated poly(methyl methacrylate) microspheres. Using a coherent undulator X-ray beam with 8.10 keV photon energy, 14 tomograms at a resolution of ∼30 nm were measured consecutively, which resulted in an accumulated dose of 30 GGy. The three-dimensional images confirmed that the polymer core was strongly affected by the absorbed dose, giving pronounced mass loss. Specifically, as the metal–polymer composite was exposed to the X-ray beam, a bubble-like region of reduced density grew within the composite, almost filling the entire volume within the thin metallic shell in the last tomogram. The bubble seemed to have its initiation point at a hole in the metal coating, emphasizing that the free polymer surface plays an important role in the degradation process. The irradiation of an uncoated polystyrene microsphere gave further evidence for mass loss at the free surface as the radius decreased with increased dose. The CXDI study was complemented by X-ray photon correlation spectroscopy, which proved efficient in establishing exposure dose limits. Our results demonstrate that radiation-induced structural changes at the tens of nanometer scale in soft materials can be followed as a function of dose, which is important for the further development of soft-matter technology.

Injection molded polymer parts are known to exhibit structural gradients of crystallinity, crystallite phases and crystallite orientations. The structural variations depend on the geometry, the material properties, and the processing conditions, and affect the mechanical properties of the molded part. We explore the use of raster-scanning small- and wide-angle X-ray scattering (SAXS, WAXS) for mapping the microstructure in dogbone specimens of an isotactic polypropylene (PP) homopolymer and a talc-reinforced isotactic PP compound. The specimens were injection molded with different mold temperatures and injection speeds, and the mapping approach revealed systematic structural heterogeneities and asymmetries. Accompanying numerical simulations of the injection molding process yielded predictions of the flow pattern, including the shear rate distribution and the resulting orientation of the flake-shaped talc particles. We found a clear correspondence between the experimentally observed data and the simulations, in particular regarding the asymmetry of the orientation distributions relative to the center of the dogbone cross section, caused by asymmetric flow through the entrance of the mold. Furthermore, the shear rate distribution correlated with the occurrence of α- and β-phases. Subtle differences in the crystallized structures along the long axis of the dogbones suggest an explanation to the observation that the specimens studied always tended to break at the same position in tensile tests. The results clearly demonstrate the potential of mapping experiments which combine lateral resolution on macroscopic length scales with the molecular-scale resolution from scattering. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014, 52, 1157–1167

Optimizing the morphology of bulk heterojunctions is known to significantly improve the photovoltaic performance of organic solar cells, but available quantitative imaging techniques are few and have severe limitations. We demonstrate X-ray ptychographic coherent diffractive imaging applied to all-organic blends. Specifically, the phase-separated morphology in bulk heterojunction photoactive layers for organic solar cells, prepared from a 50:50 blend of poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM) and thermally treated for different annealing times is imaged to high resolution. Moreover, using a fast-scanning calorimetry chip setup, the nano-morphological changes caused by repeated thermal annealing applied to the same sample could be monitored. X-ray ptychography resolves to better than 100 nm the phase-segregated domains of electron donor and electron acceptor materials over a large field of view within the active layers. The quantitative phase contrast images further allow us to estimate the local volume fraction of PCBM across the photovoltaically active layers. The volume fraction gradient for different regions provides insight on the PCBM diffusion across the depletion zone surrounding PCBM aggregates. Phase contrast X-ray microscopy is under rapid development, and the results presented here are promising for future studies of organic-organic blends, also under in situ conditions, e.g., for monitoring the structural stability during UV-Vis irradiation. © 2016 Patil et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

Chemotherapy treatment usually involves the delivery of fluorouracil (5-Fu) together with other drugs through central venous catheters. Catheters and their connectors are increasingly treated with silver or argentic alloys/compounds. Complications arising from broken catheters are common, leading to additional suffering for patients and increased medical costs. Here, we uncover a likely cause of such failure through a study of the surface chemistry relevant to chemotherapy drug delivery, i.e. between 5-Fu and silver. We show that silver catalytically decomposes 5-Fu, compromising the efficacy of the chemotherapy treatment. Furthermore, HF is released as a product, which will be damaging to both patient and catheter. We demonstrate that graphene surfaces inhibit this undesirable reaction and would offer superior performance as nanoscale coatings in cancer treatment applications.