Processing of Haynes® 282® Alloy by Direct Energy Deposition with Arc and Wire.

Direct energy deposition with arc and wire (DED-AW) is a versatile, low-cost, and energy-efficient technology for additive manufacturing of medium- and large-sized metallic components. In this study, the effects of arc energy and shielding gas in cold metal transfer (CMT) welding of walls and blocks on cooling time, mechanical properties, and macro- and microstructure have been studied using precipitation-hardenable Ni-based superalloy Haynes® 282®. The arc energy and consequently the cooling rate were varied by changing the wire feed rate and the travel speed. As expected, increasing the arc energy leads to higher cooling times for the walls. Due to the 2D thermal conduction, the thin walls cool down much slower than multi-layer welded blocks, but this reduces the strength values only very slightly. While the walls have no sensitivity to the occurrence of unacceptable seam irregularities, the multi-layer blocks show isolated seam defects, such as hot cracks or lack of fusion. Despite shielding gas variation, the as-welded blocks show acceptable strength properties at room temperatures (RT) and impact values at RT and -196 °C. However, the use of an N-containing shielding gas results in lower elongation and notched bar impact energy. Precipitation-hardened specimens tested at 871 °C exhibit a similar strength level to transverse tensile specimens of gas metal arc welding (GMAW) welded joints on 12.7 mm thick plates with fracture in the weld metal.

Tilt and shift polymorphism in molecular perovskites.

Molecular perovskites, i.e. ABX3 coordination polymers with a perovskite structure, are a chemically diverse material platform for studying fundamental and applied materials properties such as barocalorics and improper ferroelectrics. Compared to inorganic perovskites, the use of molecular ions on the A- and X-site of molecular perovskites leads to new geometric and structural degrees of freedom. In this work we introduce the concept of tilt and shift polymorphism, categorising irreversible perovskite-to-perovskite phase transitions in molecular perovskites. As a model example we study the new molecular perovskite series [(nPr)3(CH3)N]M(C2N3)3 with M = Mn2+, Co2+, Ni2+, and nPr = n-propyl, where different polymorphs crystallise in the perovskite structure but with different tilt systems depending on the synthetic conditions. Tilt and shift polymorphism is a direct ramification of the use of molecular building units in molecular perovskites and as such is unknown for inorganic perovskites. Given the role of polymorphism in materials science, medicine and mineralogy, and more generally the relation between physicochemical properties and structure, the concept introduced herein represents an important step in classifying the crystal chemistry of molecular perovskites and in maturing the field.

Defect Engineering of Copper Paddlewheel-Based Metal-Organic Frameworks of Type NOTT-100: Implementing Truncated Linkers and Its Effect on Catalytic Properties.

A series of new defect-engineered metal-organic frameworks (DEMOFs) were synthesized by framework doping with truncated linkers employing the mixed-linker approach. Two tritopic defective (truncated) linkers, biphenyl-3,3',5-tricarboxylates (LH) lacking a ligating group and 5-(5-carboxypyridin-3-yl)isophthalates (LPy) bearing a weaker interacting ligator site, were integrated into the framework of Cu2(BPTC) (NOTT-100, BPTC = biphenyl-3,3',5,5'-tetracarboxylates). Incorporating LH into the framework mainly generates missing metal node defects, thereby obtaining dangling COOH groups in the framework. However, introducing LPy forms more modified metal nodes featuring reduced and more accessible Cu sites. In comparison with the pristine NOTT-100, the defect-engineered NOTT-100 (DE-NOTT-100) samples show two unique features: (i) functional groups (the protonated carboxylate groups as the Brønsted acid sites or the pyridyl N atoms as the Lewis basic sites), which can act as second active sites, are incorporated into the MOF frameworks, and (ii) more modified paddlewheels, which provided extra coordinatively unsaturated sites, are generated. The cooperative functioning of the above characteristics enhances the catalytic performance of certain types of reactions. For a proof of concept, two exemplary reactions, namely, the cycloaddition of CO2 with propylene oxide to propylene carbonate and the cyclopropanation of styrene, were carried out to evaluate the catalytic activities of those DE-NOTT-100 materials depending on the defect structure.

A new polar perovskite coordination network with azaspiroundecane as A-site cation.

ABX3 perovskite coordination networks are a rapidly growing sub-class of crystalline coordination networks. At present, synthetic efforts in the field are dominated by the use of commercially available building blocks, leaving the potential for tuning properties via targeted compositional changes largely untouched. Here we apply a rational crystal engineering approach, using 6-azaspiro[5.5]undecane ([ASU]+) as A-site cation for the synthesis of the polar perovskite [ASU][Cd(C2N3)3].

Mechanical properties of the ferroelectric metal-free perovskite [MDABCO](NH4)I3.

The metal-free hybrid organic-inorganic perovskite [MDABCO](NH4)I3 (with MDABCO = N-methyl-1,4-diazabicyclo[2.2.2]octane) was recently discovered to exhibit an excellent ferroelectric performance, challenging established ceramic ferroelectrics. We here probe the mechanical properties of [MDABCO](NH4)I3 by combining high pressure single crystal X-ray diffraction and nanoindentation, underlining the exceptional role and opportunities that come with the use of sustainable, metal-free perovskite ferroelectrics.

Comparative study of the dynamics of lipid membrane phase decomposition in experiment and simulation.

Phase decomposition in lipid membranes has been the subject of numerous investigations by both experiment and theoretical simulation, yet quantitative comparisons of the simulated data to the experimental results are rare. In this work, we present a novel way of comparing the temporal development of liquid-ordered domains obtained from numerically solving the Cahn-Hilliard equation and by inducing a phase transition in giant unilamellar vesicles (GUVs). Quantitative comparison is done by calculating the structure factor of the domain pattern. It turns out that the decomposition takes place in three distinct regimes in both experiment and simulation. These regimes are characterized by different rates of growth of the mean domain diameter, and there is quantitative agreement between experiment and simulation as to the duration of each regime and the absolute rate of growth in each regime.

Production and characterization of plutonium dioxide particles as a quality control material for safeguards purposes.

Plutonium (Pu) dioxide particles were produced from certified reference material (CRM) 136 solution (CRM 136-plutonium isotopic standard, New Brunswick Laboratory, Argonne, IL, U.S.A., 1987) using an atomizer system on December 3, 2009 after chemical separation of americium (Am) on October 27, 2009. The highest density of the size distribution of the particles obtained from 312 particles on a selected impactor stage was in the range of 0.7-0.8 µm. The flattening degree of 312 particles was also estimated. The isotopic composition of Pu and uranium (U) and the amount of Am were estimated by thermal ionization mass spectrometry (TIMS), inductively coupled plasma mass spectrometry (ICPMS), and α-spectrometry. Within uncertainties the isotopic composition of the produced particles is in agreement with the expected values, which were derived from the decay correction of the Pu isotopes in the CRM 136. The elemental ratio of Am to Pu in the produced particles was determined on the 317th and 674th day after Am separation, and the residual amount of Am in the solution was estimated. The analytical results of single particles by micro-Raman-scanning electron microscopy (SEM)-energy-dispersive X-ray spectrometry (EDX) indicate that the produced particles are Pu dioxide. Our initial attempts to measure the density of two single particles gave results with a spread value accompanied by a large uncertainty.