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Organosilicas With Chiral Bridges And Self-Generating Mesoporosity, Andreas Ide, Rebecca Voss, Gudrun Scholz, Geoffrey A. Ozin, Markus Antonietti, Arne Thomas
Organosilicas With Chiral Bridges And Self-Generating Mesoporosity, Andreas Ide, Rebecca Voss, Gudrun Scholz, Geoffrey A. Ozin, Markus Antonietti, Arne Thomas
Rebecca Cademartiri
Amine-functionalized, chiral mesoporous organosilicas were prepared from a rationally designed precursor, which combines the functions of a network builder, a chiral latent functional group, and a porogen in one molecule. The precursors are formed by a convenient enantioselective hydroboration using (S)-monoisopinocampheylborane on an ethylene-bridged silica precursor. These precursors do self-organize when hydrolysis of their inorganic moiety takes place via an aggregation of their organic moiety into hydrophobic domains. After a condensation−ammonolysis sequence mesoporous organosilicas functionalized with chiral amine groups are obtained, with the complete chiral functionalities located at the pore wall surface and therefore accessible to chemical processes. The pore …
A Sum Frequency Generation Vibrational Spectroscopic Study Of The Adsorption And Reactions Of C6 Hydrocarbons At High Pressures On Pt(100), Kaitlin M. Bratlie, Gabor A. Somorjai
A Sum Frequency Generation Vibrational Spectroscopic Study Of The Adsorption And Reactions Of C6 Hydrocarbons At High Pressures On Pt(100), Kaitlin M. Bratlie, Gabor A. Somorjai
Kaitlin M. Bratlie
Sum frequency generation (SFG) vibrational spectroscopy was used to investigate the adsorption geometries and surface reactions of various C6 hydrocarbons (n-hexane, 2-methylpentane, 3-methylpentane, and 1-hexene) on Pt(100). At 300 K and in the presence of excess hydrogen, n-hexane, 3-methylpentane, and 2-methylpentane adsorb molecularly on Pt(100) mostly in “flat-lying” conformations. Upon heating the metal surface to 450 K, the molecules underwent dehydrogenation to form new surface species in “standing-up” conformations, such as hexylidyne and metallacyclic species.
Thermal Effects On Mechanical Grinding-Induced Surface Texture In Tetragonal Piezoelectrics, Wonyoung Chang, Alexander H. King, Keith J. Bowman
Thermal Effects On Mechanical Grinding-Induced Surface Texture In Tetragonal Piezoelectrics, Wonyoung Chang, Alexander H. King, Keith J. Bowman
Alexander H. King
The effect of temperature on grinding-induced texture in tetragonal lead zirconate titanate (PZT) and lead titanate (PT) has been investigated using in situ x-ray diffraction (XRD) with an area detector. In contrast with previous results on electrical poling, mechanically-ground PT and soft PZT materials retain strong ferroelastic textures during thermal cycling, even after excursions to temperatures slightly above the Curie temperature. The relationship between the residual stresses in the surface region, caused by grinding, and those resulting from domain wall motion is elucidated by in situ texture measurements obtained during thermal cycling.
How Surface Stresses Lead To Size-Dependent Mechanics Of Tensile Deformation In Nanowires, M. Ravi Shankar, Alexander H. King
How Surface Stresses Lead To Size-Dependent Mechanics Of Tensile Deformation In Nanowires, M. Ravi Shankar, Alexander H. King
Alexander H. King
It has been proposed that surface and interface stresses can modify the elastic behavior in nanomaterials such as nanowires. The authors show that surface stresses modify the tensile response of nanowires only when nonlinear elastic effects become important leading to cross terms between the applied stress and the surface stress. These effects are only significant when the radius of the nanowire is of the order of a few nanometers. The resulting alteration of tensile stiffness, though effected in part by the nonlinear elastic modulus, is particularly wrought by a modification of the stress state in the deformed nanowire.
Effect Of The Lattice Crystallinity On The Electron−Phonon Relaxation Rates In Gold Nanoparticles, Wenyu Huang, Wei Qian, Mostafa El-Sayed
Effect Of The Lattice Crystallinity On The Electron−Phonon Relaxation Rates In Gold Nanoparticles, Wenyu Huang, Wei Qian, Mostafa El-Sayed
Wenyu Huang
In order to study the importance of surface phonons on the electron−phonon relaxation in plasmonic nanoparticles, the effect of size, shape, and materials have recently been studied. Gold and silver nanoparticles have shown no dependence on size and shape while copper nanoparticles have shown some size dependence. This suggests that the bulk phonons, which are sensitive to the bulk-phase structure, are solely responsible for the relaxation of the hot electron in gold and silver plasmonic nanoparticles. The importance of bulk phonons should depend on the degree of crystallinity. In the present study, we have found that the electron−phonon relaxation rate …
On The Universal Scaling Behavior Of The Distance Decay Of Plasmon Coupling In Metal Nanoparticle Pairs: A Plasmon Ruler Equation, Prashant K. Jain, Wenyu Huang, Mostafa A. El-Sayed
On The Universal Scaling Behavior Of The Distance Decay Of Plasmon Coupling In Metal Nanoparticle Pairs: A Plasmon Ruler Equation, Prashant K. Jain, Wenyu Huang, Mostafa A. El-Sayed
Wenyu Huang
Localized surface plasmon resonances (LSPR) in lithographically fabricated gold (Au) nanodisc pairs are investigated using microabsorption spectroscopy and electrodynamic simulations. In agreement with previous work, we find that the fractional plasmon wavelength shift for polarization along the interparticle axis decays nearly exponentially with the interparticle gap. In addition, we find that the decay length is roughly about 0.2 in units of the particle size for different nanoparticle size, shape, metal type, or medium dielectric constant. The near-exponential distance decay and the interesting “universal” scaling behavior of interparticle plasmon coupling can be qualitatively explained on the basis of a dipolar-coupling model …
The Effect Of Plasmon Field On The Coherent Lattice Phonon Oscillation In Electron-Beam Fabricated Gold Nanoparticle Pairs, Wenyu Huang, Wei Qian, Prashant K. Jain, Mostafa El-Sayed
The Effect Of Plasmon Field On The Coherent Lattice Phonon Oscillation In Electron-Beam Fabricated Gold Nanoparticle Pairs, Wenyu Huang, Wei Qian, Prashant K. Jain, Mostafa El-Sayed
Wenyu Huang
By using electron beam lithography, we fabricated pairs of gold nanoparticles with varying interparticle separation. Double-beam femtosecond transient absorption spectroscopy was used to determine the coherent lattice oscillation frequency as a function of the interparticle separation in the presence of the plasmon field excited by the monitoring probe light. We found that the fractional shift in the coherent lattice phonon oscillation frequency follows an exponential decay with respect to the interparticle gap scaled by the disc diameter with the same decay constant as that previously observed for the fractional shift in the surface plasmon electronic oscillation resonance frequency. This strongly …
Carbazolyl Nitrenium Ion: Electron Configuration And Antiaromaticity Assessed By Laser Flash Photolysis, Trapping Rate Constants, Product Analysis, And Computational Studies, Arthur Winter, Harry H. Gibson, Daniel E. Falvey
Carbazolyl Nitrenium Ion: Electron Configuration And Antiaromaticity Assessed By Laser Flash Photolysis, Trapping Rate Constants, Product Analysis, And Computational Studies, Arthur Winter, Harry H. Gibson, Daniel E. Falvey
Arthur Winter
Laser flash photolysis of 1-(carbazol-9-yl)-2,4,6-trimethylpyridinium tetrafluoroborate generates the carbazolyl nitrenium ion (τ = 333 ns, kobs = 3.0 × 106 M-1s-1) having absorption bands at 570 and 620 nm in CH3CN. The nitrenium ion is found to have reactivity comparable to structurally similar closed-shell diarylnitrenium ions, but spectroscopic evidence favors an open-shell singlet diradical assignment for the observed nitrenium ion. The carbazolyl nitrenium ion is also more reactive than diarylnitrenium ions as a likely result of antiaromatic character. Ab initio and hybrid DFT calculations were performed to address the degree of antiaromaticity in this and similar nitrenium ions through analysis …
Benzylic Cations With Triplet Ground States: Computational Studies Of Aryl Carbenium Ions, Silylenium Ions, Nitrenium Ions, And Oxenium Ions Substituted With Meta Π Donors, Arthur Winter, Daniel E. Falvey, Christopher J. Cramer, Benjamin F. Gherman
Benzylic Cations With Triplet Ground States: Computational Studies Of Aryl Carbenium Ions, Silylenium Ions, Nitrenium Ions, And Oxenium Ions Substituted With Meta Π Donors, Arthur Winter, Daniel E. Falvey, Christopher J. Cramer, Benjamin F. Gherman
Arthur Winter
Density functional theory (B3LYP/6-31G(d,p)) was used to predict the effect of meta substitution on aryl cationic (Ar−X+) species, including aryloxenium ions, arylsilylenium ions, arylnitrenium ions, and arylcarbenium ions. Multireference second-order perturbation theory (CASPT2) calculations were used to benchmark the quantitative accuracy of the DFT calculations for representative systems. Substituting the meta positions on these species with π donors stabilizes a π,π* diradical state analogous to the well-known m-xylylene diradical. Notably, the 3,5-bis(N,N-dimethylamino)benzyl cation is predicted to have a triplet ground state by 1.9 kcal/mol by DFT and to have essentially degenerate singlet−triplet states at the CASPT2(10,9) level of theory. Adding …
Posterminaries: After Nabarro, Alexander H. King
Posterminaries: After Nabarro, Alexander H. King
Alexander H. King
With the passing of Frank Nabarro in July of this year, we have lost one of the founding fathers of materials science. His name appears in many of the textbooks from which we train our students today, and also on the spines of several volumes on dislocation theory, including his classic monograph on the subject. He rightly stands among the gods of our field. Ninety years old at his death, he was a sprightly dancer at the frontiers of knowledge, right up to the end.
Posterminaries: The Scales Of Judgement, Alexander H. King
Posterminaries: The Scales Of Judgement, Alexander H. King
Alexander H. King
Materials scientists are generally well-versed in physics, and physics, above all, is a science of measurements. The first instinct of a physicist is to parse a problem in terms of its measurables in the dimensions of mass, length, and time, and it is the shifting of attention down the scale of length that particularly characterizes our present times as the Nano Age.
Dynamics Of Surface Catalyzed Reactions; The Roles Of Surface Defects, Surface Diffusion, And Hot Electrons, Gabor Somorjai, Kaitlin Bratlie, Max Montano, Jeong Park
Dynamics Of Surface Catalyzed Reactions; The Roles Of Surface Defects, Surface Diffusion, And Hot Electrons, Gabor Somorjai, Kaitlin Bratlie, Max Montano, Jeong Park
Kaitlin M. Bratlie
The mechanism that controls bond breaking at transition metal surfaces has been studied with sum frequency generation (SFG), scanning tunneling microscopy (STM), and catalytic nanodiodes operating under the highpressure conditions. The combination of these techniques permits us to understand the role of surface defects, surface diffusion, and hot electrons in dynamics of surface catalyzed reactions. Sum frequency generation vibrational spectroscopy and kinetic measurements were performed under 1.5 Torr of cyclohexene hydrogenation/dehydrogenation in the presence and absence of H2 and over the temperature range 300-500 K on the Pt(100) and Pt(111) surfaces. The structure specificity of the Pt(100) and Pt(111) surfaces …
Posterminaries: Plain Text, Alexander H. King
Posterminaries: Plain Text, Alexander H. King
Alexander H. King
You just can’t win an argument with an English professor.
Gold Nanoparticles Propulsion From Surface Fueled By Absorption Of Femtosecond Laser Pulse At Their Surface Plasmon Resonance, Wenyu Huang, Wei Qian, Mostafa A. El-Sayed
Gold Nanoparticles Propulsion From Surface Fueled By Absorption Of Femtosecond Laser Pulse At Their Surface Plasmon Resonance, Wenyu Huang, Wei Qian, Mostafa A. El-Sayed
Wenyu Huang
Femtosecond laser irradiation of assembled nanoprisms on a quartz substrate at their strong absorbing surface plasmon resonance frequency causes their propulsion from the substrate. SEM and AFM show that the particles fly while keeping their prismatic shape, but they decrease in size by an amount that can be calculated assuming atomic sublimation. Several mechanisms are mentioned, but the sublimation mechanism, which rapidly builds up pressure under the particle and propels it away from substrate, is discussed in detail. From the kinetic energy given to the flying nanoparticle, an initial velocity of ∼160 m/s (∼360 miles/h) is calculated. The dependence of …
Thermal Effects On Domain Orientation Of Tetragonal Piezoelectrics Studied By In Situ X-Ray Diffraction, Wonyoung Chang, Alexander H. King, Keith J. Bowman
Thermal Effects On Domain Orientation Of Tetragonal Piezoelectrics Studied By In Situ X-Ray Diffraction, Wonyoung Chang, Alexander H. King, Keith J. Bowman
Alexander H. King
Thermal effects on domain orientation in tetragonal lead zirconate titanate (PZT) and lead titanate (PT) have been investigated by using in situ x-ray diffraction with an area detector. In the case of a soft PZT, it is found that the texture parameter called multiples of a random distribution (MRD) initially increases with temperature up to approximately 100 °C and then falls to unity at temperatures approaching the Curie temperature, whereas the MRD of hard PZT and PT initially undergoes a smaller increase or no change. The relationship between the mechanical strain energy and domain wall mobility with temperature is discussed.
Solid-Solid Phase Transformation Via Internal Stress-Induced Virtual Melting, Significantly Below The Melting Temperature. Application To Hmx Energetic Crystal, Valery I. Levitas, Bryan F. Henson, Laura B. Smilowitz, Blaine W. Asay
Solid-Solid Phase Transformation Via Internal Stress-Induced Virtual Melting, Significantly Below The Melting Temperature. Application To Hmx Energetic Crystal, Valery I. Levitas, Bryan F. Henson, Laura B. Smilowitz, Blaine W. Asay
Valery I. Levitas
We theoretically predict a new phenomenon, namely, that a solid−solid phase transformation (PT) with a large transformation strain can occur via internal stress-induced virtual melting along the interface at temperatures significantly (more than 100 K) below the melting temperature. We show that the energy of elastic stresses, induced by transformation strain, increases the driving force for melting and reduces the melting temperature. Immediately after melting, stresses relax and the unstable melt solidifies. Fast solidification in a thin layer leads to nanoscale cracking which does not affect the thermodynamics or kinetics of the solid−solid transformation. Thus, virtual melting represents a new …
Nmr Studies Of Lysozyme Surface Accessibility By Using Different Paramagnetic Relaxation Probes, Andrea Bernini, Ottavia Spiga, Vincenzo Venditti, Filippo Prischi, Luisa Bracci, Angela Pui-Ling Tong, Wing-Tak Wong, Neri Niccolai
Nmr Studies Of Lysozyme Surface Accessibility By Using Different Paramagnetic Relaxation Probes, Andrea Bernini, Ottavia Spiga, Vincenzo Venditti, Filippo Prischi, Luisa Bracci, Angela Pui-Ling Tong, Wing-Tak Wong, Neri Niccolai
Vincenzo Venditti
Paramagnetic probes, whose approach to proteins can be monitored by nuclear magnetic resonance (NMR) studies, have been found to be of primary relevance for investigating protein surfaces' accessibility. Here, a Gd(III) neutral complex which contains two metal ions, [Gd2(L7)(H2O)2], is suggested as a paramagnetic probe particularly suited for systematic NMR investigation of protein surface accessibility, due to an expected high relaxivity and to the lack of electric charge which could favor specific interactions. Hen egg white lysozyme has been used as a model system to verify the absence of preferential approaches of this paramagnetic probe to specific protein moieties by …
Synthesis And Characterization Of Highly Amine Functionalized Mesoporous Organosilicas By An “All-In-One” Approach, Rebecca Voss, Arne Thomas, Markus Antonietti, Geoffrey A. Ozin
Synthesis And Characterization Of Highly Amine Functionalized Mesoporous Organosilicas By An “All-In-One” Approach, Rebecca Voss, Arne Thomas, Markus Antonietti, Geoffrey A. Ozin
Rebecca Cademartiri
Mesoporous organosilicas (MOs) represent a promising class of organic–inorganic nanocomposites for a broad range of applications like catalysis, sensing, separation, or microelectronics. Their distinct feature is the presence of organic groups incorporated into the channel walls of a mesoporous structure. Here, we present a convenient “all-in-one” approach using silsesquioxane surfactant precursors for the functionalization of the channel walls with primary amine groups. The monomer is made by a hydroboration/aminolysis sequence on the base of a commercial monomer, with the template bound to the functionalization site by hydroboration and released after silica condensation and aminolysis. This combination ensures both the placement …
Size-Driven Domain Reorientation In Hydrothermally Derived Lead Titanate Nanoparticles, Zhiyuan Ye, Elliot B. Slamovich, Alexander H. King
Size-Driven Domain Reorientation In Hydrothermally Derived Lead Titanate Nanoparticles, Zhiyuan Ye, Elliot B. Slamovich, Alexander H. King
Alexander H. King
High-resolution transmission electron microscopy studies of hydrothermally derived platelike lead titanate nanoparticles reveal that below a critical size of approximately 70 nm, the single ferroelectric domain polarization axis reorients from perpendicular to parallel to the plate. We suggest that during particle growth, ions in the hydrothermal processing medium compensate for the ferroelectric depolarization energy. When the processing medium is removed by washing and drying, single domain nanoparticles minimize their depolarization energy by c-axis flipping.
Mechanism Of Structural Transformation In Bismuth Titanate, Sudhanshu Mallick, Keith J. Bowman, Alexander H. King
Mechanism Of Structural Transformation In Bismuth Titanate, Sudhanshu Mallick, Keith J. Bowman, Alexander H. King
Alexander H. King
Sodium-doped bismuth titanate undergoes a transformation from Bi4Ti3O12 to Na0.5Bi4.5Ti4O15 on heating in air at temperatures exceeding 800 °C. This transformation proceeds through the intermediate Na0.5Bi8.5Ti7O27 structure which is an intergrowth phase of the two. High-resolution transmission electron microscopy was used to study this transformation. From the Moiré pattern that was obtained, the crystallographic orientation of the transformation front has been determined and a mechanism is proposed for this structural transformation.
Photothermal Reshaping Of Prismatic Au Nanoparticles In Periodic Monolayer Arrays By Femtosecond Laser Pulses, Wenyu Huang, Wei Qian, Mostafa A. El-Sayed
Photothermal Reshaping Of Prismatic Au Nanoparticles In Periodic Monolayer Arrays By Femtosecond Laser Pulses, Wenyu Huang, Wei Qian, Mostafa A. El-Sayed
Wenyu Huang
Prismatic goldnanoparticles in the periodic monolayer arrays prepared with nanosphere lithography technique can be reshaped with femtosecond laser pulses at different powers and wavelengths. As the power density of 400 nm femtosecond laser increases, the prismatic particle tips begin to round and the overall particle shape changes from a prism to a sphere with a tripodal intermediate. The formation of the tip-rounded nanoprisms is probably due to the dewetting properties of gold on quartz surface and the low melting temperature at the tips. The formation of the tripodal nanoparticles is attributed to the inhomogeneous heating and lattice rearrangement of the …
The Optically Detected Coherent Lattice Oscillations In Silver And Gold Monolayer Periodic Nanoprism Arrays: The Effect Of Interparticle Coupling, Wenyu Huang, Wei Qian, Mostafa A. El-Sayed
The Optically Detected Coherent Lattice Oscillations In Silver And Gold Monolayer Periodic Nanoprism Arrays: The Effect Of Interparticle Coupling, Wenyu Huang, Wei Qian, Mostafa A. El-Sayed
Wenyu Huang
Using femtosecond transient spectroscopy, we studied the optically detected laser-induced coherent phonon oscillation of monolayers of periodic arrays of prismatic-shaped silver and gold nanoparticles, assembled by using the technique of nanosphere lithography. In this method, the same size of polystyrene sphere and the same vacuum conditions are used. Under these circumstances, the gold nanoprisms formed are found to have sharper tips than the corresponding silver nanoprisms. For both gold and silver nanoparticles, the surface plasmon absorption maximum is found to depend linearly on size. The coherent lattice oscillation periods are also found to depend linearly on size. However, although the …
Dislocation-Indenter Interaction In Nanoindentation, M. Ravi Shankar, Alexander H. King, Srinivasan Chandrasekar
Dislocation-Indenter Interaction In Nanoindentation, M. Ravi Shankar, Alexander H. King, Srinivasan Chandrasekar
Alexander H. King
A formulation of dislocation-indenter interaction in two-dimensional, isotropic elasticity is presented. A significant dislocation-indenter interaction is predicted when dislocations are nucleated very close to the indenter. This interaction is expected to have an important influence on dislocation motion and multiplication. Upon nucleation close to the indenter, the dislocations are shown to modify the load, load distribution, and moment acting on the indenter. This effect is seen to vary with the indentation contact length. Further away from the indenter, the indenter-dislocation interaction is shown to be negligible.
Coherent Vibrational Oscillation In Gold Prismatic Monolayer Periodic Nanoparticle Arrays, Wenyu Huang, Wei Qian, Mostafa A. El-Sayed
Coherent Vibrational Oscillation In Gold Prismatic Monolayer Periodic Nanoparticle Arrays, Wenyu Huang, Wei Qian, Mostafa A. El-Sayed
Wenyu Huang
We studied the ultrafast laser-induced coherent phonon oscillation in prismatic shaped gold nanoparticles assembled in monolayer periodic arrays by using the nanosphere lithographic technique. The amplitude and phase of the oscillation observed by ultrafast pump−probe transient spectroscopy is monitored as the wavelength of the dipolar surface plasmon absorption decreases. At a certain wavelength, the oscillation could not be observed. As the monitoring wavelength decreases further, the sign of the amplitude changes. From the wavelength at which the oscillation is not detected, the dependence of the absorption maxima on the size of the nanoparticles, the changes in the nanoparticle size are …
Photochemical Generation Of Nitrenium Ions From Protonated 1,1-Diarylhydrazines, Arthur Winter, Selina I. Thomas, Andrew C. Kung, Daniel E. Falvey
Photochemical Generation Of Nitrenium Ions From Protonated 1,1-Diarylhydrazines, Arthur Winter, Selina I. Thomas, Andrew C. Kung, Daniel E. Falvey
Arthur Winter
Laser flash photolysis experiments, chemical trapping studies, and time-dependent density functional theory calculations demonstrate that photolysis of protonated 1,1-diarylhydrazines generates N,N-diarylnitrenium ions.
Effect Of Meta Electron-Donating Groups On The Electronic Structure Of Substituted Phenyl Nitrenium Ions, Arthur Winter
Effect Of Meta Electron-Donating Groups On The Electronic Structure Of Substituted Phenyl Nitrenium Ions, Arthur Winter
Arthur Winter
Density functional theory (UB3LYP/6-31G(d,p)) was used to determine substituent effects on the singlet−triplet-state energy gap for 21 meta-substituted phenylnitrenium ions. It was found that strongly electron-donating substituents stabilize the triplet state relative to the singlet state. With sufficiently strong meta electron donors (e.g., m,m‘-diaminophenylnitrenium ion) the triplet is predicted to be the ground state. Analysis of equilibrium geometries, Kohn−Sham orbital distributions, and Mulliken spin densities for the triplet states of this series of nitrenium ions leads to the conclusion that there are two spatially distinct types of low-energy triplet states. Simple arylnitrenium ions such as phenylnitrenium ions as well as …
Heterostructures Of Polymer Photonic Crystal Films, Marc Egen, Rebecca Voss, Bernd Griesebock, Rudolf Zentel, Sergei Romanov, Clivia Sotomayor Torres
Heterostructures Of Polymer Photonic Crystal Films, Marc Egen, Rebecca Voss, Bernd Griesebock, Rudolf Zentel, Sergei Romanov, Clivia Sotomayor Torres
Rebecca Cademartiri
This paper describes ways to multilayer opaline films (opaline heterostructures) composed from functional opal layers of spheres with different lattice constants. At first various monodisperse colloidsboth cross-linked and un-cross-linkedwere prepared from methyl methacrylate, methyl α-chloroacrylate, and methyl α-bromoacrylate. These colloids can be crystallized into large, well-oriented opaline films with the help of a “drawing apparatus” by the method of crystallization in a moving meniscus. After annealing, a second opaline film can be crystallized on top of these films and so on. Electron microscopy inspection shows a sharp borderline between the sublayers and no disorder on both sides although the lattice …
Low-Cost Manufacturing Process For Nanostructured Metals And Alloys, Travis L. Brown, Srinivasan Swaminathan, Srinivasan Chandrasekar, W. Dale Compton, Alexander H. King, Kevin P. Trumble
Low-Cost Manufacturing Process For Nanostructured Metals And Alloys, Travis L. Brown, Srinivasan Swaminathan, Srinivasan Chandrasekar, W. Dale Compton, Alexander H. King, Kevin P. Trumble
Alexander H. King
In spite of their interesting properties, nanostructured materials have found limited uses because of the cost of preparation and the limited range of materials that can be synthesized. It has been shown that most of these limitations can be overcome by subjecting a material to large-scale deformation, as occurs during common machining operations. The chips produced during lathe machining of a variety of pure metals, steels, and other alloys are shown to be nanostructured with grain (crystal) sizes between 100 and 800 nm. The hardness of the chips is found to be significantly greater than that of the bulk material.
Dispersion Of Potassium Nitrate And The Resulting Strong Basicity On Zirconia, Ying Wang, Wenyu Huang, Yuan Chun, Jia Rong Xia, Jian Hua Zhu
Dispersion Of Potassium Nitrate And The Resulting Strong Basicity On Zirconia, Ying Wang, Wenyu Huang, Yuan Chun, Jia Rong Xia, Jian Hua Zhu
Wenyu Huang
A novel solid superbase is derived from zirconia-supported potassium nitrate. Dispersion and decomposition of potassium nitrate on zirconia were investigated and compared with that on alumina to explore the effect of the support on the preparation of solid strong bases. Spontaneous dispersion capacity of KNO3 on ZrO2 was found to be 8.1 K+ nm-2, very close to that of a vacant site on ZrO2. An unusually strong basicity was generated on ZrO2 through decomposition of the loaded KNO3 that began around 613 K, enhancing the catalytic activity of ZrO2 in cis-but-2-ene isomerization at 273 K. Moreover, KNO3/ZrO2 samples, except 34% …
Synthesis And Characterization Of Potassium-Modified Alumina Superbases, Ying Wang, Jian Hua Zhu, Wenyu Huang
Synthesis And Characterization Of Potassium-Modified Alumina Superbases, Ying Wang, Jian Hua Zhu, Wenyu Huang
Wenyu Huang
Novel solid superbases can be prepared by dispersing potassium salts such as K2CO3 and KHCO3 on alumina followed by thermal treatments. The resulting materials show an extremely high activity in the isomerization of cis-but-2-ene at 0°C and possess base strength of at least H− = + 26.5. X-Ray diffraction (XRD) and Raman spectra of K2CO3 or KHCO3 modified alumina reveal the formation of potassium hydroalumina carbonate, which is the precursor of active species. Decomposition of potassium salts on alumina has been studied by use of thermal gravimetric differential thermal analysis (TG-DTA) and temperature programmed decomposition-mass spectrometry (TPDE-MS). Two CO2 evolution …