A modified criterion for shear band formation in bulk metallic glass under complex stress states

A new criterion for shear band formation in metallic glasses is proposed based on the shear plane criterion proposed by Packard and Schuh [1]. This modified shear plane (MSP) criterion suggests that a shear band is not initiated randomly throughout the entire material under stress but is initiated at the physical boundaries or defects and at locations where the highest normal stress modified maximum shear stress occurs. Moreover, the same as in the shear plan criterion, the shear stress all over the shear band should exceed the shear yield strength of the material. For a complete shear band to form, both requirements need to be fulfilled. The shear yield strength of the material is represented by the shear stress of the point at which the shear band stops. The new criterion agrees very well with experimental results in both the determination of the shear yield strength and the shear band path. (C) 2010 Elsevier B.V. All rights reserved.

Metallic glass nanofilms

In this paper, we report for the first time the spontaneous formation of Zr-based metallic glass nanofilms by developed dynamic forced-shear-rupture technique of hat-shaped specimens. The obtained nanofilms have about 100 nm thickness and other two geometrical dimensions can reach micrometer scales. Their glassy nature and structural stability were solidly identified. It was found that electrons with the wavelength of less than 0.165 Å could make the metallic glass nanofilms transparent. Furthermore, it is clearly shown that shearbanding instability still afflicts such 100-nm-thick metallic glass nanofilms.

Strain rate-dependent shear band behavior in bulk metallic glasses

In this article, we review our recent advances in understanding the deformation behavior of a typical tough Zr41.2Ti13.8Cu12.5Ni10Be22.5 (Vit 1) bulk metallic glass (BMG), as a model material, under various loading modes and strain rates, focusing particularly on the rate-dependence and formation mechanism of shear-banding. Dynamic and quasi-static mechanical experiments, including plate shear, shear punch and spherical indentation, and continuum as well as atomistic modeling on shear-banding are discussed. The results demonstrate that higher strain rate slows down the annihilation process of free volume, but promotes the free-volume coalescence, which is responsible for the rate-dependent shear banding. The physical origin of shear bands, that is the free volume softening underpinned by irreversible rearrangements of atoms, is unveiled. Finally, some concluding remarks are given.

Fracture behavior of a Zr-metallic glass under dynamic compression

Dynamic planar compressive experiments on a typical tough Zr-BMG (Bulk Metallic Glass) were carried out under impact velocity of 500-600 m/sec and strain rate of 10(6)/s. The fracture surface of samples exhibits different fracture patterns at different parts of the sample. At a corner close to the front loading boundary, fracture patterns from the free edge toward the centre changed from equiaxial veins in microscale to periodic corrugations in nanoscale; in the middle of the sample, the fracture surface contains glazed zones laid out orderly along the same boundary. FEM simulation was performed to investigate the stress distributions in the impacted sample under a short duration impact loading. It has revealed that the fracture patterns changing from the free edge toward the centre were resulted from the fracture modes' changing from the tensile dominant fracture to the shear dominant fracture. Whereas at the middle part of the sample, fracture initiated from several parallel shear bands propagating close to the same boundary is due to a large strain or much higher shear stress in this area.

EFFECT OF STRUCTURAL RELAXATION ON THE DEFORMATION BEHAVIOR OF A Zr64.13Cu15.75Ni10.12Al10 BULK METALLIC GLASS UNDER NANOINDENTATION

Structural relaxation by isothermal annealing below the glass transition temperature is conducted on a Zr64.13Cu15.75Ni10.12Al10 bulk metallic glass. The effect of structural relaxation on thermal and mechanical properties was investigated by differential scanning calorimetry and instrumented nanoindentation. The recovery of the enthalpy in the DSC curves indicates that thermally unstable defects were annihilated through structural relaxation. During nanoindentation, the structural relaxation did not have a significant influence on the serrated plastic flow behavior. However, Structural relaxation shows an obvious effect in increasing both the hardness and elastic modulus, which is attributed to the annihilation of thermally unstable defects that resulted from the relaxation.

Chiral synthesis on catalysts immobilized in microporous and mesoporous materials

This paper reviews the recent progress made in the asymmetric synthesis on chiral catalysts in porous materials and discusses the effects of surface and pores on enantio-selectivity (confinement effect). This paper also summarizes various approaches of immobilization of the chiral catalysts onto surfaces and into pores of solid inorganic supports such as microporous and mesoporous materials. The most important reactions surveyed for the chiral synthesis in porous materials include epoxidation. hydrogenation, hydroformylation, Aldol and Diels-Alder reactions, etc. The confinement effect originated from the surfaces and the pores turns out to be a general phenomenon. which may make the enantioselectivity increase (positive effect) or decrease (negative effect). The confinement effect becomes more pronounced particularly when the bonding between the catalyst and the surface is more rigid and the pore size is tuned to a suitable range. It is proposed that the confinement in chiral synthesis is essentially a consequence of subtle change in transition states induced by weak-interaction in pores or on surfaces. It is also anticipated that the enantioselectivity could be improved by tuning the confinement effect based on the molecular designing of the pore/surface and the immobilized catalysts according to the requirements of chiral reactions.

The research of rheology and thermodynamics of organic-inorganic hybrid membrane during the membrane formation

To clarify the mechanism of organic-inorganic hybrid membrane formation by phase-inversion method, the thermodynamical and theological properties of PSF/TiO2 casting solution were investigated by the viscosity measurement and the triangle phase diagram, respectively. TiO2 introduction decreased the non-solvent tolerance of casting solution with non-solvent 20% ethanol aqueous solution, which caused thermodynamic enhancement of phase separation, and also resulted in the change of theological properties from Newtonian fluid to non-Newtonian fluid and the viscosity increase of casting solution, which induced rheological hindrance in demixing process

Controlled synthesis of organic-inorganic hybrid nanofibers by a wet-chemical route

Organic-inorganic hybrid nanofibers are successfully synthesized by incorporating 3,3 ',5,5 '-tetramethylbenzidine (TMB) and H2PtCl6 at room temperature. The morphology and size can be simply controlled by tuning the molar ratio and initial concentration of reactants. A possible formation mechanism was suggested on the basis of the experimental results. The optical properties were investigated and the as-obtained product displays a strong fluorescence emission at room temperature that may be promising for applications in the fabrication of photoelectric materials. (C) 2008 Elsevier B.V. All rights reserved.

Synthesis and Characterization of Urea Bridged Hybrid Periodic Mesoporous Organosilica Materials

Urea bridged organic-inorganic hybrid mesoporous SiO2 materials (U-BSQMs) were synthesized through a sol-gel procedure by co-condensation of bis(triethoxysilyl propyl) urea (BSPU) under basic conditions using cetyltrimethylammonium bromide (CTAB) as organic template. X-ray diffraction (XRD) and transmission electron microscopy (TEM) confirmed the mesoporous structure of the sample. Fourier-transform infrared spectroscopy (FT-IR), solid state CP-MAS NMR spectroscopy of Si-29 (Si-29, CP-MAS NMR) and C-13 (C-13 CP NMR) indicated that most of the Si-C bonds are unbroken during the synthesis process.

Silica Materials Doped with Bifunctional Ionic Liquid Extractant for Yttrium Extraction

Two new silica-based organic-inorganic hybrid materials (B104SGs and O104SGs) doped with a binary mixture of imidazolium and phosphonium ionic liquids have been synthesized and used as sorbents in batch system for rare earths (RE) separation. Imidazolium ionic liquids 1-butyl-3-methylimidazolium hexafluorophosphate (C(4)mim(+)PF(6)(-)) or 1-octyl-3-methylimidazolium hexafluorophosphate (C(8)mim(+)PF(6)(-)) acted as porogens to prepare porous materials and additives to stabilize extractant within silica gel.

A study on the near-infrared luminescent properties of xerogel materials doped with dysprosium complexes

A series of dysprosium complex doped xerogels with the same first ligand (acac = acetylacetone) and different neutral ligands were synthesized in situ via a sol-gel process. The Fourier transform infrared (FTIR) spectra, diffuse reflectance (DR) spectra, and near-infrared (NIR) luminescent properties of dysprosium complexes and dysprosium complex doped xerogels are described in detail. The results reveal that the dysprosium complex is successfully synthesized in situ in the corresponding xerogel. Excitation at the maximum absorption wavelength of the ligands resulted in the characteristic NIR luminescence of the Dy3+ ion, which contributes to the energy transfer from the ligands to the central Dy3+ ion in both the dysprosium complexes and xerogels via an antenna effect.

Construction and Photoluminescence of Monophase Hybrid Materials Derived from a Urea-Based Bis-Silylated Bipyridine

A urea-based bis-silylated bipyridine ligand derived from 4,4'-diamino-2,2'-bipyridine has been prepared. Organic-inorganic hybrid materials with a high loading of lanthanide 2,2-bipyridine moieties were obtained by using the silylated bipyridine as the only siloxane network precursor in the presence of lanthanide ions (or lanthanide complexes). The in-situ formation of lanthanide complexes from lanthanide ions and the silylated bipyridine during the sol-gel processing was confirmed by the luminescence behavior of the obtained hybrid materials and that of the corresponding pure lanthanide complex [Ln(bpy)(2)Cl-3 center dot 2H(2)O].

Novel Near-Infrared Luminescent Hybrid Materials Covalently Linking with Lanthanide [Nd(III), Er(III), Yb(III), and Sm(III)] Complexes via a Primary beta-Diketone Ligand: Synthesis and Photophysical Studies

A series of novel, colorless, and transparent sot-gel derived hybrid materials Ln-DBM-Si covalently grafted with Ln(DBM-OH)(3)center dot 2H(2)O (where DBM-OH = o-hydroxydibenzoylmethane, Ln = Nd, Er, Yb, and Sin) were prepared through the primary beta-diketone ligand DBM-OH. The structures and optical properties of Ln-DBM-Si were studied in detail. The investigation results revealed that the lanthanide complexes were successfully in situ grafted into the corresponding hybrids Ln-DBM-Si. Upon excitation at the maximum absorption of ligands, the resultant materials displayed excellent near-infrared luminescence.

Thiacalix[4]arene-Supported Planar Ln(4) (Ln = Tb-III, Dy-III) Clusters: Toward Luminescent and Magnetic Bifunctional Materials

This paper reports the syntheses, crystal structures, and luminescent and magnetic properties of four tetranuclear Tb-III (1 and 3) and Dy-III (2 and 4) complexes supported by p-phenylthiacalix[4]arene (H(4)PTC4A) and p-tert-butylthiacalix-[4]arene (H(4)TC4A). All four frameworks can be formulated as [Ln(4)(III)(PTC4A/TC4A)(2)(mu(4)-OH)Cl-3(CH3OH)(2)(H2O)(3)], and some methanol and water solvent molecules are occupied in the interstices. The compounds are featured with a sandwichlike unit constructed by two tail-to-tail calixarene molecules and a planar tetragonal (mu(4)-OH)Ln(4) cluster. The photoluminescent analyses suggest that there is an efficient ligand-to-Ln(III) energy transfer for compounds 1-3 and H(4)PTC4A is a more efficient "antenna" than H(4)TC4A.

Organic-inorganic hybrid material for the cells immobilization: Long-term viability mechanism and application in BOD sensors

In this paper, organic-inorganic hybrid material, which is composed of silica and the grafting copolymer of poly (vinyl alcohol) and 4-vinylpyridine (PVA-g-P(4-VP)), was employed to immobilize Trichosporon cutaneum strain 2.570 cells. Cells entrapped into the hybrid material were found to keep a long-term viability. The mechanism of such a long-term viability was investigated by using confocal laser scanning microscopy (CLSM). Our studies revealed that arthroconidia produced in the extracellular material might play an important role in keeping the long-term viability of the immobilized microorganism. After the arthroconidia were activated, an electrochemical biochemical oxygen demand (BOD) sensor based on cell/hybrid material-modified supporting membrane was constructed for verifying the proposed mechanism.