Chemical Engineering Commons^™

A Computational Investigation Of The Interstitial Oxidation Thermodynamics Of A Mo-Nb-Ta-W High Entropy Alloy Beyond The Dilute Regime, Adib J. Samin

Faculty Publications

High entropy alloys (HEAs) are promising candidates for high-temperature structural material applications. Oxidation is a major factor that must be accounted for when designing such materials and it is thus important to study the oxidation behavior of HEAs to enable the optimum design of next generation materials. In this study, the thermodynamic behavior of interstitial oxygen in a Mo-Nb-Ta-W high entropy alloy was explored beyond the dilute limit. This was accomplished by sampling configurations of the HEA and HEA-oxygen systems from an isothermal–isobaric ensemble using a series of first-principle-based Monte Carlo simulations. It was found that the interstitial oxygen had …

Microstructures And Hardness Of Tig Welded Experimental 57fe15cr25ni Steel, Parikin Parikin, Mohammad Dani, Abu Khalid Rivai, Agus Hadi Ismoyo, Riza Iskandar, Arbi Dimyati

Makara Journal of Technology

The microstructures and hardness of tungsten inert gas (TIG) welded experimental 57Fe15Cr25Ni steel were investigated through optical–scanning electron microscopy analyses and with a hardness tester, respectively. The welding process restructured the constituent atoms into regular and irregular crystal lattices. Rapid cooling of the weld metal allowed the formation of a dendritic (columnar) structure, with porous grains. By contrast, slow cooling influenced HAZ and led to the formation of grain structures. The crystal lattice became more organized and larger than other zones. Meanwhile, the base metal formed circular nets that covered large area inside thick and thin grain boundaries. The diffraction …

Improving The Thermal Stability Of Cellobiohydrolase Cel7a From Hypocrea Jecorina By Directed Evolution, Frits Goedegebuur, Lydia Dankmeyer, Peter Gualfetti, Saeid Karkehabadi, Henrik Hansson, Suvamay Jana, Vicky Huynh, Bradley R. Kelemen, Paulien Kruithof, Edmund A. Larenas, Pauline J. M. Teunissen, Jerry Ståhlberg, Christina M. Payne, Colin Mitchinson, Mats Sandgren

Chemical and Materials Engineering Faculty Publications

Secreted mixtures of Hypocrea jecorina cellulases are able to efficiently degrade cellulosic biomass to fermentable sugars at large, commercially relevant scales. H. jecorina Cel7A, cellobiohydrolase I, from glycoside hydrolase family 7, is the workhorse enzyme of the process. However, the thermal stability of Cel7A limits its use to processes where temperatures are no higher than 50 °C. Enhanced thermal stability is desirable to enable the use of higher processing temperatures and to improve the economic feasibility of industrial biomass conversion. Here, we enhanced the thermal stability of Cel7A through directed evolution. Sites with increased thermal stability properties were combined, and …

Composition And Work Function Relationship In Os–Ru–W Ternary Alloys, Phillip D. Swartzentruber, Michael J. Detisch, Thomas John Balk

Chemical and Materials Engineering Faculty Publications

Os–Ru thin films with varying concentrations of W were sputter deposited in order to investigate their structure–property relationships. The films were analyzed with x-ray diffraction to investigate their crystal structures, and a Kelvin probe to investigate their work functions. An Os–Ru–W film with ∼30 at. % W yielded a work function maximum of approximately 5.38 eV. These results align well with other studies that found work function minima from thermionic emission data on M-type cathodes with varying amounts of W in the coatings. Furthermore, the results are consistent with other work explaining energy-level alignment and charge transfer of molecules on …

Influence Of Crystal Structure On The Electrochemical Performance Of A-Site-Deficient Sr 1-Xnb 0.1 Co 0.9 O 3-Δ Perovskite Cathodes, Yinlong Zhu, Ye Lin, Xuan Shen, Jaka Sunarso, Wei Zhou, Shanshan Jiang, Dong Su, Fanglin Chen, Zongping Shao

Faculty Publications

The creation of A-site cation defects within a perovskite oxide can substantially alter the structure and properties of its stoichiometric analogue. In this work, we demonstrate that by vacating 2 and 5% of A-site cations from SrNb_0.1Co_0.9O_3−δ (SNC1.00) perovskites (Sr_1−sNb_0.1Co_0.9O_3−δ, s = 0.02 and 0.05; denoted as SNC0.98 and SNC0.95, respectively), a Jahn–Teller (JT) distortion with varying extents takes place, leading to the formation of a modified crystal lattice within a the perovskite framework. Electrical conductivity, electrochemical performance, chemical compatibility and microstructure of Sr …

Homochiral Metal-Organic Materials: Design, Synthetic And Enantioseletive Separation, Shi-Yuan Zhang

USF Tampa Graduate Theses and Dissertations

Owing to the growing demand for enantiopurity in biological and chemical processes, tremendous efforts have been devoted to the synthesis of homochiral metal-organic materials (MOMs) because of their potential applications in chiral separation and asymmetric catalysis. In this dissertation, the synthetic strategies for homochiral MOMs are discussed keeping the focus on their applications. Two distinct approaches have been taken to synthesize chiral structures with different topologies and accessible cavities. The chiral MOMs have been utilized in enantioselective separation of racemates.

Chiral variants of the prototypal metal-organic framework MOF-5, δ-CMOF-5 and [lambda]-CMOF-5, have been synthesized by preparing MOF-5 in the presence …

A New Open-Framework Iron Borophosphate From Ionic Liquids: Kfe[Bp2o8(Oh)], Guangmei Wang, Anja V. Mudring

Anja V. Mudring

A new open-framework iron borophosphate, KFe[BP2O8(OH)], has been obtained by ionothermal synthesis from KH2PO4, FeCl3∙4H2O, H3BO3 and [C4mpyr]Br (1-butyl-1-methylpyrrolidinium bromide). Single-crystal X-ray diffraction analysis shows that KFe[BP2O8(OH)] (monoclinic, P21/c, a = 9.372(2) Å , b = 8.146(2)Å , c = 9.587(2) Å, β = 101.18(3)°, V = 718.0(2)Å3 and Z = 4) has a three-dimensional (3-D) framework structure composed by {Fe(III)O5(OH)} octahedra as well as {BO3(OH)} and {PO4} tetrahedra. As anionic structural sub-unit, KFe[BP2O8(OH)], contains an infinite open-branched {[BP2O8(OH)]4-} chain which is formed by alternating {BO3(OH)} and {PO4} tetrahedra. {Fe(III)O5(OH)} octahedra share common O corners with five phosphate tetrahedra and …

The First Lanthanide Telluride-Bromide: La3te4br, A Valence Compound, Markus Larres, Anja V. Mudring, Gerd Meyer

Anja V. Mudring

The first ternary lanthanide telluride-bromide La3Te4Br was obtained from a mixture of LaTe and LaBr3 (in the presence of iridium) in a sealed tantalum container at elevated temperatures. The crystal structure (orthorhombic, Pnma, a = 1634.3(2), b = 435.0(1), c = 1426.6(2) pm, Z = 4, R1 (I0 > 2s(I0)) = 0.0349) is built from dicapped trigonal prisms of tellurium and bromine atoms surrounding lanthanum in two different ways. The dicapped trigonal prisms are connected via common edges to a threedimensional structure, in the same fashion as is known for the binary U3Te5. La3Te4Br is a valence compound according to (La3+)3(Te2-)4(Br-) …

(B15c5)Bii3(I2): Molecular Benzo-15-Crown-5―Bii3 Complexes Bridged By Iodine Molecules To Chains, Christoph Fiolka, Mark Richter, Ingo Pantenburg, Anja V. Mudring, Gerd Meyer

Anja V. Mudring

The reaction of bismuth triiodide with iodine and benzo-15-crown-5 in ethanol/dichloromethane yielded red single crystals of (b15c5)BiI3(I2) (monoclinic, P21/c (no. 14), a = 1376.9(1), b = 1172.7(1), c = 1700.2(2) pm, b = 115.197(6), V = 2484.1(4)·106 pm3, Z = 4). Neutral pseudo-octahedral complexes (b15c5)BiI3 are connected by secondary bonding interactions via iodine molecules to chains. Electronic structure calculations of the neutral complex (b15c5)BiI3 reveal that the compound can indeed be described as b15c5 interacting with a molecular BiI3 unit. However, bonding has to be mainly electrostatic as the interactions of the bismuth 6s lone pair with the 2p orbitals …

The Syntheses And Electrochemical Performance Of Nano-Mno_2 For Supercapacitor, Jun Ma, Ming-Sen Zheng, Quan-Feng Dong

Journal of Electrochemistry

Nano-manganese dioxide were prepared by two different methods which are low temperature solid reaction and chemical deposition.The products were characterized by XRD,SEM,BET and constant current charge-discharge tests.The result shows that there is a close relationship between specific capacitance and BET surface areas.Meanwhile the specific capacitance was impacted little by the structure of the nano-manganese dioxides.However,the product performance of high rates,was influenced by structure,the higher rate can be obtained with the more perfect crystal structure.

Symmetry Breaking Of In-Plane Order In Confined Copolymer Mesophases, G. E. Stein, Eric W. Cochran, K. Katsov, G. H. Fredrickson, E. J. Kramer, X. Li, J. Wang

Eric W. Cochran

Packing of spherical-domain block copolymer mesophases confined to a thin film is investigated as a function of the number of layers n. We find an abrupt transition from hexagonal to orthorhombic in-plane ordering of domains when n is increased from 4 to 5. As n increases further (up to 23 in this study), the symmetry of the orthorhombic phase asymptotically approaches that of the body-centered cubic (110) plane. These results are interpreted in terms of the energetics of competing packings in the bulk and at the film interfaces. Detailed structural and thermodynamic properties are obtained with self-consistent field theory.

Effect Of Chain Architecture And Surface Energies On The Ordering Behavior Of Lamellar And Cylinder Forming Block Copolymers, V. Khanna, Eric W. Cochran, A. Hexemer, G. E. Stein, G. H. Fredrickson, E. J. Kramer, X. Li, J. Wang, S. F. Hahn

Eric W. Cochran

We investigate the effect of surface energy and chain architecture on the orientation of microdomains in relatively thick films (600-800 nm) of lamellar and cylindrical block copolymers of poly(cyclohexylethylene) (C) and poly(ethylene) (E). The E block has 26 ethyl branches per 1000 backbone carbon atoms. Melt surface energies of the C and E blocks are 22.3 and 20.9 mJ/m 2, respectively. Grazing-incidence small-angle X-ray scattering (GISAXS), scanning force microscopy (SFM), and cross-sectional transmission electron microscopy (TEM) show that cylindrical and lamellar CEC triblock copolymers orient their microdomains normal to the surface throughout the film thickness. However, a lamellar CE diblock …

Semicrystalline Thermoplastic Elastomeric Polyolefins: Advances Through Catalyst Development And Macromolecular Design, Atsushi Hotta, Eric W. Cochran, Janne Ruokolainen, Vikram Khann, Glenn H. Fredrickson, Edward J. Kramer, Yong-Woo Shin, Fumihiko Shimizu, Anna E. Cherian, Phillip D. Hustad, Jeffrey M. Rose, Geoffrey W. Coates

Eric W. Cochran

We report the design, synthesis, morphology, phase behavior, and mechanical properties of semicrystalline, polyolefin-based block copolymers. By using living, stereoselective insertion polymerization catalysts, syndiotactic polypropylene-block-poly(ethylene-co-propylene)-block-syndiotactic polypropylene and isotactic poly propylene-block-regioirregular poly propylene-block- isotactic polypropylene triblock copolymers were synthesized. The volume fraction and composition of the blocks, as well as the overall size of the macromolecules, were controlled by sequential synthesis of each block of the polymers. These triblock copolymers, with semicrystalline end-blocks and mid-segments with low glass-transition temperatures, show significant potential as thermoplastic elastomers. They have low Young's moduli, large strains at break, and better than 90% elastic recovery at …

Tethered Nano Building Blocks: Toward A Conceptual Framework For Nanoparticle Self-Assembly, Zhenli Zhang, Mark A. Horsch, Monica H. Lamm, Sharon C. Glotzer

Monica H. Lamm

We perform molecular simulations to study the self-assembly of nanoparticles functionalized with oligomeric tethers attached to specific locations on the nanoparticle surface. We demonstrate that for certain categories of tethered nano building blocks the obtained morphologies may be predicted using concepts from block copolymer microphase separation and liquid-crystal phase ordering, whereas for other categories the unique packing constraints introduced by nanoparticle geometry and by nanoparticle-tether topology lead to structures far richer than those found in conventional block copolymer, surfactant, and liquid-crystal systems. Our results suggest the potential usefulness of considering tethered nano building blocks as a new class of "macromolecule" …