Comprehensive characterization of the structure of Zr-based metallic glasses.

Structure of metallic glasses fascinates as the generic amorphous structural template for ubiquitous systems. Its specification necessitates determination of the complete hierarchical structure, starting from short-range-order (SRO) → medium-range-order (MRO) → bulk structure and free volume (FV) distribution. This link has largely remained elusive since previous investigations adopted one-technique-at-a-time approach, focusing on limited aspects of any one domain. Reconstruction of structure from experimental data inversion is non-unique for many of these techniques. As a result, complete and precise structural understanding of glass has not emerged yet. In this work, we demonstrate the first experimental pathway for reconstruction of the integrated structure, for Zr 67 Ni 33 and Zr 52 Ti 6 Al 10 Cu 18 Ni 14 glasses. Our strategy engages diverse (× 7) multi-scale techniques [XAFS, 3D-APT, ABED/NBED, FEM, XRD, PAS, FHREM] on the same glass. This strategy complemented mutual limitations of techniques and corroborated common parameters to generate complete, self-consistent and precise parameters. Further, MRO domain size and inter-void separation were correlated to identify the presence of FV at MRO boundaries. This enabled the first experimental reconstruction of hierarchical subset: SRO → MRO → FV → bulk structure. The first ever image of intermediate region between MRO domains emerged from this link. We clarify that determination of all subsets is not our objective; the essence and novelty of this work lies in directing the pathway towards finite solution, in the most logical and unambiguous way.

Liquid like nucleation in free-standing nanoscale films.

The concept of a critical nucleus size (r*) is of pivotal importance in phase transformations involving nucleation and growth. The current investigation pertains to crystallization in nanoscale thin films and study of the same using high resolution lattice fringe imaging (HRLFI) and finite element simulations. Using the CuZrAl bulk metallic glass system as a model system for this study, we demonstrate a liquid like nucleation behaviour in nanoscale free-standing films upon heating. The r* for the formation of the Cu10Zr7 phase in thin films (of decreasing thickness) approaches that of the r* for the formation of the crystal from a liquid (i.e.). Working in the nucleation dominant regime, we introduce the concept of 'depth sensitive lattice fringe imaging'. The thickness of the film is determined by electron energy loss spectroscopy and the strain energy of the system is computed using finite element computations.

Investigation of short-range structural order in Zr69.5Cu12Ni11Al7.5 and Zr41.5Ti41.5Ni17 glasses, using X-ray absorption spectroscopy and ab initio molecular dynamics simulations.

Short-range order has been investigated in Zr69.5Cu12Ni11Al7.5 and Zr41.5Ti41.5Ni17 metallic glasses using X-ray absorption spectroscopy and ab initio molecular dynamics simulations. While both of these alloys are good glass formers, there is a difference in their glass-forming abilities (Zr41.5Ti41.5Ni17 > Zr69.5Cu12Ni11Al7.5). This difference is explained by inciting the relative importance of strong chemical order, icosahedral content, cluster symmetry and configuration diversity.

Synthesis, structures and DFT calculations of 2-(4,6-dimethyl pyrimidyl)selenolate complexes of Cu(I), Ag(I) and Au(I) and their conversion into metal selenide nanocrystals.

The complexes [M{SeC4H(Me-4,6)2N2}]6 (M = Cu (1), Ag (2)) and [Au{SeC4H(Me-4,6)2N2}(PEt3)] (3) have been prepared and characterized by elemental analyses, UV-vis, NMR ((1)H, (13)C, (77)Se) spectroscopy and single crystal X-ray diffraction. The crystal structures of [Cu{SeC4H(Me-4,6)2N2}]6·H2O (1·H2O), [Ag{SeC4H(Me-4,6)2N2}]6·6MeOH·H2O (2·6MeOH·H2O) and [Au{SeC4H(Me-4,6)2N2}(PEt3)] (3) revealed that their metal centers acquire distorted square-pyramidal, trigonal and linear geometries, respectively. DFT calculations have been carried out to rationalize nuclearity in copper(i) chalcogenolate complexes. The calculations suggest that there is hardly any energy difference between the tetrameric and hexameric forms. Thermal behavior of [Cu{SeC4H(Me-4,6)2N2}]6 was studied by thermogravimetric analysis. Thermolysis of [M{SeC4H(Me-4,6)2N2}]6 (M = Cu, Ag) in 1-dodecanethiol (DDT) at 150 °C gave a cubic phase of Cu7Se4 and an orthorhombic phase of Ag2Se, respectively. Copper selenide (Cu7Se4) thin films were deposited on glass and silicon substrates by using [Cu{SeC4H(Me-4,6)2N2}]6 at 400 °C by AACVD.

Uptake of hazardous radionuclides within layered chalcogenide for environmental protection.

Ensuring environmental protection in and around nuclear facilities is a matter of deep concern. Toward this, layered chalcogenide with CdI2 crystal structure has been prepared. Structural characterizations of layered chalcogenide suggest 'topotactic ionic substitution' as the dominant mechanism behind uptake of different cations within its lattice structure. An equilibration time of 45 min and volume to mass ratio of 30:1 are found to absorb (233)U, (239)Pu, (106)Ru, (85+89)Sr, (137)Cs and (241)Am radionuclides to the maximum extents.

Diorganotin(IV) 2-pyridyl selenolates: synthesis, structures and their utility as molecular precursors for the preparation of tin selenide nanocrystals and thin films.

Reactions of R(2)SnCl(2) (R = Me, Et, (t)Bu) with NaSeC(5)H(3)(R'-3)N (R' = H or Me) gave complexes of the composition [R(2)Sn{2-SeC(5)H(3)(R'-3)N)}(2)], which on treatment with R(2)SnCl(2) afforded chloro complexes, [R(2)Sn{2-SeC(5)H(3)(R'-3)N}Cl]. These complexes were characterized by elemental analyses and UV-vis and NMR ((1)H, (13)C, (77)Se and (119)Sn) spectroscopy. The crystal structures of [R(2)Sn(SeC(5)H(4)N)(2)] (R = Me or (t)Bu) and [Me(2)Sn{2-SeC(5)H(3)(Me-3)N}Cl] were determined by single crystal X-ray diffraction. The tin atom in the former two structures acquires a skew trapezoidal configuration, whereas in the latter it adopts a distorted trigonal bipyramidal geometry. Thermolysis of [R(2)Sn(2-SeC(5)H(4)N)(2)] (R = Me, Et or (t)Bu) and [Et(2)Sn{2-SeC(5)H(3)(Me-3)N}(2)] in oleylamine (OA) afforded tin selenide nanostructures. Thin films of SnSe were deposited on glass and silicon substrates by the AACVD of [(t)Bu(2)Sn(2-SeC(5)H(4)N)(2)]. The nanostructures and thin films were characterized by XRD, EDX, AFM, SEM, TEM and SAED techniques. The photovoltaic properties of the thin films have been evaluated.

Copper(I) 2-pyridyl selenolates and tellurolates: synthesis, structures and their utility as molecular precursors for the preparation of copper chalcogenide nanocrystals and thin films.

The complexes, [Cu{EC(5)H(3)(R-3)N}](4) (E/R = Se/Me or Te/R; R = H or Me) were isolated by the reaction between CuCl and NaEC(5)H(3)(R-3)N and were characterized by elemental analyses, uv-vis and NMR ((1)H, (13)C) spectroscopy. The crystal structures of [Cu{SeC(5)H(3)(Me-3)N}](4) and [Cu(TeC(5)H(4)N)](4) revealed that the molecules are tetrameric in which each copper atom lies at the vertex of the tetrahedron and each face of the tetrahedron is capped by the bridging pyridylchalcogenolate ligand. Thermal behavior of these complexes was studied by thermogravimetric analysis. Depending on reaction conditions, thermolysis gave both stoichiometric and non-stoichiometric copper chalcogenides, which were characterized by XRD, EDX, SEM, TEM and SAED techniques. These precursors were used for the preparation of nanocrystals and for deposition of thin films of copper chalcogenides by AACVD (Aerosol Assisted Chemical Vapor Deposition).

2-Pyridyl selenolates of antimony and bismuth: Synthesis, characterization, structures and their use as single source molecular precursor for the preparation of metal selenide nanostructures and thin films.

Reactions of SbCl(3) and BiCl(3) with M'Se-C(5)H(3)(R-3)N (M' = Li or Na; R = H or Me) gave homoleptic selenolate complexes of the general formula [M{Se-C(5)H(3)(R-3)N}(3)] (M = Sb or Bi). The complexes were characterized by elemental analysis, UV-vis and NMR ((1)H, (13)C and (77)Se) spectroscopy. The single crystal X-ray analysis of [M{Se-C(5)H(3)(Me-3)N}(3)].nH(2)O (M/n = Sb/1.5 and Bi/0.5) revealed that the antimony complex adopts a trigonal pyramidal configuration with monodentate selenolate ligands while the bismuth analogue acquires a distorted square pyramidal configuration defined by two chelating and one monodentate selenolate groups. Pyrolysis of [M{Se-C(5)H(3)(Me-3)N}(3)] either in a furnace or in hexadecylamine (HDA) at different temperatures gave a variety of M(2)Se(3) nanostructures. Thin films of metal selenides have also been deposited on glass substrate by aerosol-assisted chemical vapor deposition (AACVD). Both nanostructures and thin films of metal selenides were characterized by UV-vis spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX) and transmission electron microscopy (TEM).

Phacoemulsification in vitrectomised eyes / 国际眼科杂志(Guoji Yanke Zazhi)

Purpose To report our experience of phacoemulsification in patients who had previously undergone parsplana vitrectomysurgery. Methods Medical records of 26 consecutive cases of phacoemulsification operated on between July 1994 and July 1998, who hadpreviously undergone parsplana vitrectomy, were retrospectively analysed. Patient demographics, the initial indication and number ofparsplana surgeries, type of cataract and preoperative visual acuity were noted for all patients. The intraoperative, early, and latepostoperative complications were analysed. The final visual acuity and its correlation to the preoperative potential acuity meter (PAM)visual acuity were analysed. Results Outof26, 24 were males and 2 were females, ranging in age from19 to 63 years. 18patients(69.2%) had undergone parsplana vitrectomy once, 7 (26.9%) twice and (3.8%) three times. Proliferative diabetic retinopathy (38.5%) andretinal detachment (23.7%) were the common indications for parsplana vitrectomy. Posterior subcapsular cataract was the predominanttype seen in 13 patients (50%). Intraoperative complications included small pupil in 4 (15.5%), posterior capsular break in 1 (3.8%), poorvisibility in 2 (7.7%), posterior capsular plaques in 2 (7.7%), and excessive deep anterior chamber in 2 (7.7%). The notable earlypostoperative complication was corneal edema existing at one week in 13 patients (50%) which cleared in all cases by the 4th week.Posterior capsular opacification was seen in 5 cases (19%). 9 patients had a final visual acuity of ≤ 20/100 and in 8 of these patients,significant retinal or optic nerve pathology was noted. In 13 patients, the final best corrected visual acuity was equal to or better than PAMacuity whereas in 2 cases, the best corrected visual acuity was less than the PAM acuity. Conclusions Phacoemulsification is a safe andeffective surgical procedure in post-vitrectomised eyes. Posterior subcapsular cataract is the predominant type of cataract seen in thisseries. Small pupils, posterior capsular plaques which can not be polished and excessive deep anterior chambers are commonintraoperative complications. Corneal edema and posterior capsular opacification are significant postoperative complications. Preexistingretinal or optic nerve pathology determin the final visual acuity and potential acuity meter can correctly predicts the final visual acuity inmost patients.