Revealing The Morphology of Ink and Aerosol Jet Printed Palladium-Silver Alloys Fabricated from Metal Organic Decomposition Inks.

Palladium films hold signicance due to their remarkable affinity for hydrogen diffusion, rendering them valauble for the seperation and purification of hydrogen in membrane reactors. However, palladium is expensive, and its films can become brittle after only a few cycles of hydrogen separation. Alloying with silver has been shown to overcome the problem of palladium embrittlement. Palladium-silver films have been produced via several methods but all have drawbacks, such as difficulties controlling the alloy composition. This study explores two promising jet printing methods: Inkjet and Aerosoljet. Both methods offer potential advantages such as direct patterning, which reduces waste, enables thin film production, and allows for the control of alloy composition. For the first time, palladium-silver alloys have been produced via inkjet printing using a palladium-silver metal organic decomposition (MOD) ink, which alloys at a temperature of 300 °C with nitrogen. Similarly, this study also demonstrates a pioneering approach for Aerosol Jet printing, showing the potential of a novel room-temperature method, for the deposition of palladium-silver MOD inks. This low temperature approach is considered an important development as palladium-silver MOD inks are originally designed for deposition on heated substrates.

Tensegrity Modelling and the High Toughness of Spider Dragline Silk.

This work establishes a tensegrity model of spider dragline silk. Tensegrity systems are ubiquitous in nature, being able to capture the mechanics of biological shapes through simple and effective modes of deformation via extension and contraction. Guided by quantitative microstructural characterization via air plasma etching and low voltage scanning electron microscopy, we report that this model is able to capture experimentally observed phenomena such as the Poisson effect, tensile stress-strain response, and fibre toughness. This is achieved by accounting for spider silks' hierarchical organization into microfibrils with radially variable properties. Each fibril is described as a chain of polypeptide tensegrity units formed by crystalline granules operating under compression, which are connected to each other by amorphous links acting under tension. Our results demonstrate, for the first time, that a radial variability in the ductility of tensegrity chains is responsible for high fibre toughness, a defining and desirable feature of spider silk. Based on this model, a discussion about the use of graded tensegrity structures for the optimal design of next-generation biomimetic fibres is presented.

Characterizing Cross-Linking Within Polymeric Biomaterials in the SEM by Secondary Electron Hyperspectral Imaging.

A novel capability built upon secondary electron (SE) spectroscopy provides an enhanced cross-linking characterization toolset for polymeric biomaterials, with cross-linking density and variation captured at a multiscale level. The potential of SE spectroscopy for material characterization has been investigated since 1947. The absence of suitable instrumentation and signal processing proved insurmountable barriers to applying SE spectroscopy to biomaterials, and consequently, capturing SE spectra containing cross-linking information is a new concept. To date, cross-linking extent is inferred from analytical techniques such as nuclear magnetic resonance (NMR), differential scanning calorimetry, and Raman spectroscopy (RS). NMR provides extremely localized information on the atomic scale and molecular scale, while RS information volume is on the microscale. Other methods for the indirect study of cross-linking are bulk mechanical averaging methods, such as tensile and compression modulus testing. However, these established averaging methods for the estimation of polymer cross-linking density are incomplete because they fail to provide information of spatial distributions within the biomaterial morphology across all relevant length scales. The efficacy of the SE spectroscopy capability is demonstrated in this paper by the analysis of poly(glycerol sebacate)-methacrylate (PGS-M) at different degrees of methacrylation delivering new insights into PGS-M morphology.

Making Sense of Complex Carbon and Metal/Carbon Systems by Secondary Electron Hyperspectral Imaging.

Carbon and carbon/metal systems with a multitude of functionalities are ubiquitous in new technologies but understanding on the nanoscale remains elusive due to their affinity for interaction with their environment and limitations in available characterization techniques. This paper introduces a spectroscopic technique and demonstrates its capacity to reveal chemical variations of carbon. The effectiveness of this approach is validated experimentally through spatially averaging spectroscopic techniques and using Monte Carlo modeling. Characteristic spectra shapes and peak positions for varying contributions of sp2-like or sp3-like bond types and amorphous hydrogenated carbon are reported under circumstances which might be observed on highly oriented pyrolytic graphite (HOPG) surfaces as a result of air or electron beam exposure. The spectral features identified above are then used to identify the different forms of carbon present within the metallic films deposited from reactive organometallic inks. While spectra for metals is obtained in dedicated surface science instrumentation, the complex relations between carbon and metal species is only revealed by secondary electron (SE) spectroscopy and SE hyperspectral imaging obtained in a state-of-the-art scanning electron microscope (SEM). This work reveals the inhomogeneous incorporation of carbon on the nanoscale but also uncovers a link between local orientation of metallic components and carbon form.

Exploiting Plasma Exposed, Natural Surface Nanostructures in Ramie Fibers for Polymer Composite Applications.

Nanoscale surface morphology of plant fibers has important implications for the interfacial bonding in fiber-polymer composites. In this study, we investigated and quantified the effect of plasma-surface modification on ramie plant fibers as a potential tool for simple and efficient surface modification. The extensive investigation of the effects of plasma treatment of the fiber surface nano-morphology and its effect on the fiber-polymer interface was performed by Low-Voltages Scanning Electron Microscopy (LV-SEM), infrared spectroscopy (FT-IR) analysis, fiber-resin angle measurements and mechanical (tensile) testing. The LV-SEM imaging of uncoated plasma treated fibers reveals nanostructures such as microfibrils and elementary fibrils and their importance for fiber mechanical properties, fiber wettability, and fiber-polymer matrix interlocking which all peak at short plasma treatment times. Thus, such treatment can be an effective in modifying the fiber surface characteristics and fiber-polymer matrix interlocking favorably for composite applications.

Mapping Polymer Molecular Order in the SEM with Secondary Electron Hyperspectral Imaging.

Understanding nanoscale molecular order within organic electronic materials is a crucial factor in building better organic electronic devices. At present, techniques capable of imaging molecular order within a polymer are limited in resolution, accuracy, and accessibility. In this work, presented are secondary electron (SE) spectroscopy and secondary electron hyperspectral imaging, which make an exciting alternative approach to probing molecular ordering in poly(3-hexylthiophene) (P3HT) with scanning electron microscope-enabled resolution. It is demonstrated that the crystalline content of a P3HT film is reflected by its SE energy spectrum, both empirically and through correlation with nano-Fourier-transform infrared spectroscopy, an innovative technique for exploring nanoscale chemistry. The origin of SE spectral features is investigated using both experimental and modeling approaches, and it is found that the different electronic properties of amorphous and crystalline P3HT result in SE emission with different energy distributions. This effect is exploited by acquiring hyperspectral SE images of different P3HT films to explore localized molecular orientation. Machine learning techniques are used to accurately identify and map the crystalline content of the film, demonstrating the power of an exciting characterization technique.