Panayia Ematousa II: Political, cultural, ethnic and social relations in Cyprus: Approaches to regional studies

Edited by L. Wriedt Sorensen & K. Winther Jacobse

Rational Design of Pore Size and Functionality in a Series of Isoreticular Zwitterionic Metal-Organic Frameworks

The isoreticular expansion and functionalization of charged-polarized porosity has been systematically explored by the rational design of 11 isostructural zwitterionic metal-organic frameworks (ZW-MOFs). This extended series of general structural composition {[M3F(L1)3(L2)1.5]·guests}n was prepared by employing the solvothermal reaction of Co and Ni tetrafluoroborates with a binary ligand system composed of zwitterionic pyridinium derivatives and traditional functionalized ditopic carboxylate auxiliary ligands (HL1·Cl = 1-(4-carboxyphenyl)-4,4′-bipyridinium chloride, Hcpb·Cl; or 1-(4-carboxyphenyl-3-hydroxyphenyl)-4,4′-bipyridinium chloride, Hchpb·Cl; and H2L2 = benzene-1,4-dicarboxylic acid, H2bdc; 2-aminobenzene-1,4-dicarboxylic acid, H2abdc; 2,5-dihydroxy-1,4-benzenedicarboxylic acid, H2dhbdc; biphenyl-4,4′-dicarboxylic acid, H2bpdc; or stilbene-4,4′-dicarboxylic acid, H2sdc). Single-crystal structure analyses revealed cubic crystal symmetry (I-43m, a = 31-36 Å) with a 3D pore system of significant void space (73-81%). The pore system features three types of pores being systematically tunable in size ranging from 17.4 to 18.8 Å (pore I), 8.2 to 12.8 Å (pore II), and 4.8 to 10.4 Å (pore III) by the choice of auxiliary ligands. All members of this series have noninterpenetrating structures and exhibit robust architectures, as evidenced by their permanent porosity and high thermal stability (up to 300 °C). The structural integrity and specific surface areas could be systematically optimized using supercritical CO2 exchange methods for framework activation resulting in BET surface areas ranging from 1250 to 2250 m2/g. Most interestingly, as a structural landmark, we found the pore surfaces lined with charge gradients employed by the pyridinium ligands. This key feature results in significant adsorption of carbon dioxide and methane which is attributed to polarization effects. With this contribution we pioneer the reticulation of pyridinium building blocks into extended zwitterionic networks in which specific properties can be targeted

An Evaluation of the Fe-N Phase Diagram Considering Long-Range Order of N Atoms in γ'-Fe4N1-x and ε-Fe2N1-z

The chemical potential of nitrogen was described as a function of nitrogen content for the Fe-N phases α-Fe[N], γ'-Fe4N1-x, and ε-Fe2N1-z. For α-Fe[N], an ideal, random distribution of the nitrogen atoms over the octahedral interstices of the bcc iron lattice was assumed; for γ'-Fe4N1-x and ε-Fe2N1-z, the occurrence of a long-range ordered distribution of the nitrogen atoms over the octahedral interstices of the close packed iron sublattices (fcc and hcp, respectively) was taken into account. The theoretical expressions were fitted to nitrogen-absorption isotherm data for the three Fe-N phases. The α/α + γ', α + γ'/γ', γ'/γ' + ε, and γ' + ε/ε phase boundaries in the Fe-N phase diagram were calculated from combining the quantitative descriptions for the absorption isotherms with the known composition of NH3/H2 gas mixtures in equilibrium with coexisting α and γ' phases and in equilibrium with coexisting γ' and ε phases. Comparison of the present phase boundaries with experimental data and previously calculated phase boundaries showed a major improvement as compared to the previously calculated Fe-N phase diagrams, where long-range order for the nitrogen atoms in the γ' and ε phases was not accounted for

TEM characterization and high-resolution modelling of second-phase particles of V and Ti containing TWIP steel under uniaxial hot-tensile condition

Composition and crystallographic nature of precipitates in microalloyed advanced high-strength steels (AHSS) greatly influence their microstructure and mechanical behavior. Second-phase precipitation in a high-Mn twinning-induced plasticity (TWIP) steel single microalloyed with V and Ti under uniaxial hot-tensile condition is experimentally and theoretically studied using high-resolution this purpose, carbon extraction replica technique, image treatment, and computer simulation are used to determine the crystallographic features of particles and compared with experimental measurements. Results show particle morphologies depending on crystallographic orientation, namely, hexagonal-type for TWIP-V steel and rectangular-type for TWIP-Ti steel. Measurements on particle size range from 10 to 190 nm in both steels. HRTEM digital image processing allows correcting the obtained Fast Fourier Transform (FFT) diffraction patterns, where interplanar distance measurements indicate the presence of VC and TiC compounds. In the case of the modeled particles, it is possible to identify the NaCltype crystal structure, which are correctly relate with experimental morphologies. Finally, theoretical simulations based on the multislice approach of the dynamical theory of electron diffraction allow modeling HRTEM images. Thus, results indicate that current characterization and simulation procedure are helpful in recognizing crystallographic nature of precipitates formed in the studied TWIP steels.Peer ReviewedPostprint (author's final draft

Temperature dependent CO2 behavior in microporous 1-D channels of a metal-organic framework with multiple interaction sites

The MOF with the encapsulated CO2 molecule shows that the CO2 molecule is ligated to the unsaturated Cu(II) sites in the cage using its Lewis basic oxygen atom via an angular eta(1)-(O-A) coordination mode and also interacts with Lewis basic nitrogen atoms of the tetrazole ligands using its Lewis acidic carbon atom. Temperature dependent structure analyses indicate the simultaneous weakening of both interactions as temperature increases. Infrared spectroscopy of the MOF confirmed that the CO2 interaction with the framework is temperature dependent. The strength of the interaction is correlated to the separation of the two bending peaks of the bound CO2 rather than the frequency shift of the asymmetric stretching peak from that of free CO2. The encapsulated CO2 in the cage is weakly interacting with the framework at around ambient temperatures and can have proper orientation for wiggling out of the cage through the narrow portals so that the reversible uptake can take place. On the other hand, the CO2 in the cage is restrained at a specific orientation at 195 K since it interacts with the framework strong enough using the multiple interaction sites so that adsorption process is slightly restricted and desorption process is almost clogged.ope

Status and Prospects of ZnO-Based Resistive Switching Memory Devices

In the advancement of the semiconductor device technology, ZnO could be a prospective alternative than the other metal oxides for its versatility and huge applications in different aspects. In this review, a thorough overview on ZnO for the application of resistive switching memory (RRAM) devices has been conducted. Various efforts that have been made to investigate and modulate the switching characteristics of ZnO-based switching memory devices are discussed. The use of ZnO layer in different structure, the different types of filament formation, and the different types of switching including complementary switching are reported. By considering the huge interest of transparent devices, this review gives the concrete overview of the present status and prospects of transparent RRAM devices based on ZnO. ZnO-based RRAM can be used for flexible memory devices, which is also covered here. Another challenge in ZnO-based RRAM is that the realization of ultra-thin and low power devices. Nevertheless, ZnO not only offers decent memory properties but also has a unique potential to be used as multifunctional nonvolatile memory devices. The impact of electrode materials, metal doping, stack structures, transparency, and flexibility on resistive switching properties and switching parameters of ZnO-based resistive switching memory devices are briefly compared. This review also covers the different nanostructured-based emerging resistive switching memory devices for low power scalable devices. It may give a valuable insight on developing ZnO-based RRAM and also should encourage researchers to overcome the challenges

On the nitrogen-induced lattice expansion of a non-stainless austenitic steel, Invar 36®, under triode plasma nitriding

Chromium, as a strong nitride-forming element, is widely regarded to be an “essential” ingredient for the formation of a nitrogen-expanded lattice in thermochemical nitrogen diffusion treatments of austenitic (stainless) steels. In this article, a proprietary “chrome-free” austenitic iron-nickel alloy, Invar® 36 (Fe-36Ni, in wt pct), is characterized after triode plasma nitriding (TPN) treatments at 400 °C to 450 °C and compared with a “stainless” austenitic counterpart RA 330® (Fe-19Cr-35Ni, in wt pct) treated under equivalent nitriding conditions. Cr does indeed appear to play a pivotal role in colossal nitrogen supersaturation (and hence anisotropic lattice expansion and superior surface hardening) of austenitic steel under low-temperature (≤ 450 °C) nitrogen diffusion. Nevertheless, this work reveals that nitrogen-induced lattice expansion occurs below the nitride-containing surface layer in Invar 36 alloy after TPN treatment, implying that Cr is not a necessity for the nitrogen-interstitial induced lattice expansion phenomenon to occur, also suggesting another type of γN