Interface-Driven Strain in Heavy Ion-Irradiated Zr/Nb Nanoscale Metallic Multilayers: Validation of Distortion Modeling via Local Strain Mapping.

Nanolayered metallic alloys are promising materials for nuclear applications thanks to their resistance to radiation damage. Here, we investigate the effect of ion (C, Si, and Cu) irradiation at room temperature with different fluences into sputtered Zr/Nb metallic multilayer films with periods 27 nm (thin) and 96 nm (thick). After irradiation, while a high strain in the entire thin nanoscale metallic multilayer (NMM) is observed, a quite small strain in the entire thick NMM is established. This difference is further analyzed by a semianalytical model, and the reasons behind it are revealed, which are also validated by local strain mapping. Both methods show that within a thick layer, two opposite distortions occur, making the overall strain small, whereas in a thin layer, all the atomic planes are affected by the interface and are subjected to only a single type of distortion (Nb─tension and Zr─compression). In both thin and thick NMMs, with increasing damage, the strain around the interface increases, resulting in a release of the elastic energy at the interface (decrease in the lattice mismatch), and the radiation-induced transition of the Zr/Nb interfaces from incoherent to partially coherent occurs. Density functional theory simulations decipher that the inequality of point defect diffusion flux from the inner to the interface-affected region is responsible for the presence of opposite distortions within a layer. Technologically, based on this work, we estimated that Zr/Nb55 with thicknesses around Zr = 24 nm and Nb = 31 nm is the most promising multilayer system with the high radiation damage resistance and minimum swelling for nuclear applications.

A comparative study on the physicochemical characteristics of nanoparticles released in vivo from CoCrMo tapers and cement-stem interfaces of total hip replacements.

The good biocompatibility and corrosion resistance of the bulk CoCrMo alloy has resulted in it being used in the manufacture of implants and load bearing medical devices. These devices, however, can release wear and corrosion products which differ from the composition of the bulk CoCrMo alloy. The physicochemical characteristics of the particles and the associated in vivo reactivity are dictated by the wear mechanisms and electrochemical conditions at the sites of material loss. Debris released from CoCrMo hip bearings, taper junctions, or cement-stem interfaces can, therefore, have different chemical and morphological characteristics, which provide them with different in vivo toxicities. Here, we propose to assess and compare the characteristics of the particles released in vivo from CoCrMo tapers and cement-stem interfaces which have received less attention compared to debris originating from the hip bearings. The study uses state-of-art characterization techniques to provide a detailed understanding of the size, morphology, composition, and chemistry of the particles liberated from the wear and corrosion flakes from revised hip replacements, with an enzymatic treatment. The phase analyses identified Cr2 O3 nanoparticles released from tapers and cement-stem interfaces, whose composition did not vary with origin or particle morphology. The size distributions showed significantly smaller particles were released from the stems, compared to the particles originating from the corresponding tapers. The investigation demonstrates that the tribocorrosive processes occurring at the taper and stem interfaces both result in Cr2 O3 nanoparticle formation.

Investigation of nano-sized debris released from CoCrMo secondary interfaces in total hip replacements: Digestion of the flakes.

The in vivo release of wear debris and corrosion products from the metallic interfaces of total hip replacements is associated with a wide spectrum of adverse body reactions and systemic manifestations. The origin of debris and the electrochemical conditions at the sites of material loss both play a role in determining the physicochemical characteristics of the particles, and thus influence their in vivo reactivity. Debris retrieved from revised CoCrMo tapers and cement-stem interfaces consists of heterogeneous flakes that comprise mechanically mixed metal particles, corrosion products and organic material. Detailed investigation of the size and composition of the metal debris contained within these composites requires the digestion of the flakes to release the small metal particles. Here, we compare alkaline and enzymatic digestion methods that both aim to fragment the flakes and reveal their smallest building blocks. The characterization of debris cleaned with both methods revealed crystalline Cr oxide nanoparticles and clusters. Comparison between the treatments showed that the alkaline method is more efficient in fragmenting the flakes and provided cleaner and generally smaller nanoparticles than exhibited in debris released with the enzymatic treatment. The provision of cleaner nanoparticles from the alkaline method also allows the physicochemical properties of the particles to be more clearly identified. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 107B: 424-434, 2019.

Parylene C topographic micropattern as a template for patterning PDMS and Polyacrylamide hydrogel.

Parylene C is a well-known polymer and it has been mainly employed as a protective layer for implantable electronics. In this paper, we propose a new approach to use Parylene C as a versatile template for patterning soft materials potentially applicable as scaffolds in cardiac tissue engineering (TE). Parylene C substrates were anisotropically patterned through standard lithographic process with hydrophilic channels separating raised hydrophobic strips. Ridges and grooves of the template are 10 µm width and depth ranging from 1 to 17 µm. Polydimethylsiloxane (PDMS) and Polyacrylamide (PAm) hydrogel have been chosen as soft polymers to be moulded. Thanks to their chemical and physical properties PDMS and PAm hydrogel mimic the extracellular matrix (ECM). PDMS was spin coated on micropatterned Parylene C obtaining composite substrates with 460 nm and 1.15 µm high grooves. The Young's modulus of the composite Parylene C/PDMS was evaluated and it was found to be almost half when compared to PDMS. PAm hydrogel was also printed using collagen coated micro-grooved Parylene C. Optical micrographs and fluorescence analysis show the successful topographic and protein pattern transfer on the hydrogel.

Electronic metal-support interaction enhanced oxygen reduction activity and stability of boron carbide supported platinum.

Catalysing the reduction of oxygen in acidic media is a standing challenge. Although activity of platinum, the most active metal, can be substantially improved by alloying, alloy stability remains a concern. Here we report that platinum nanoparticles supported on graphite-rich boron carbide show a 50-100% increase in activity in acidic media and improved cycle stability compared to commercial carbon supported platinum nanoparticles. Transmission electron microscopy and x-ray absorption fine structure analysis confirm similar platinum nanoparticle shapes, sizes, lattice parameters, and cluster packing on both supports, while x-ray photoelectron and absorption spectroscopy demonstrate a change in electronic structure. This shows that purely electronic metal-support interactions can significantly improve oxygen reduction activity without inducing shape, alloying or strain effects and without compromising stability. Optimizing the electronic interaction between the catalyst and support is, therefore, a promising approach for advanced electrocatalysts where optimizing the catalytic nanoparticles themselves is constrained by other concerns.

2H→1T Phase Engineering of Layered Tantalum Disulfides in Electrocatalysis: Oxygen Reduction Reaction.

Tremendous attention is currently being paid to renewable sources of energy. Transition-metal dichalcogenides (TMDs) have been intensively studied for their promising catalytic activities in the hydrogen evolution reaction (HER) and the oxygen reduction reaction (ORR). In this fundamental work, we explored the catalytic properties of TMD family members 2H TaS2 and 1T TaS2 . Our findings reveal that both polytypes exhibit poor HER performance, which is even more pronounced after electrochemical reduction/oxidation. Our experimental data show that 1T TaS2 has a lower overpotential at a current density of -10 mA cm-1 , despite theoretical DFT calculations that indicated that the more favorable free energy of hydrogen adsorption should make "perfect" 2H TaS2 a better HER catalyst. Thorough characterization showed that the higher conductivity of 1T TaS2 and a slightly higher surface oxidation of 2H TaS2 explains this discrepancy. Moreover, changes in the catalytic activity after electrochemical treatment are addressed here. For the ORR in an alkaline environment, the electrochemical treatment led to an improvement in catalytic properties. With onset potentials similar to that of Pt/C catalysts, TaS2 was found to be an efficient catalyst for the ORR, rather than for proton reduction, in contrast to the behavior of Group 6 layered TMDs.