Science.gov

Sample records for complex sheet metal

  1. Methodology development for the sustainability process assessment of sheet metal forming of complex-shaped products

    NASA Astrophysics Data System (ADS)

    Pankratov, D. L.; Kashapova, L. R.

    2015-06-01

    A methodology was developed for automated assessment of the reliability of the process of sheet metal forming process to reduce the defects in complex components manufacture. The article identifies the range of allowable values of the stamp parameters to obtain defect-free punching of spars trucks.

  2. Perforating Thin Metal Sheets

    NASA Technical Reports Server (NTRS)

    Davidson, M. E.

    1985-01-01

    Sheets only few mils thick bonded together, punched, then debonded. Three-step process yields perforated sheets of metal. (1): Individual sheets bonded together to form laminate. (2): laminate perforated in desired geometric pattern. (3): After baking, laminate separates into individual sheets. Developed for fabricating conductive layer on blankets that collect and remove ions; however, perforated foils have other applications - as conductive surfaces on insulating materials; stiffeners and conductors in plastic laminates; reflectors in antenna dishes; supports for thermal blankets; lightweight grille cover materials; and material for mockup of components.

  3. Horizontal electromagnetic casting of thin metal sheets

    DOEpatents

    Hull, John R.; Lari, Robert J.; Praeg, Walter F.; Turner, Larry R.

    1988-01-01

    Thin metal sheets are cast by magnetically suspending molten metal deposited within a ferromagnetic yoke and between AC conducting coils and linearly displacing the magnetically levitated liquid metal while it is being cooled to form a solid metal sheet. Magnetic flux increases as the molten metal sheet moves downward and decreases as the molten metal sheet moves upward to stabilize the sheet and maintain it in equilibrium as it is linearly displaced and solidified by cooling gases. A conducting shield is electrically coupled to the molten metal sheet by means of either metal sheet engaging rollers or brushes on the solidified metal, and by means of an electrode in the vessel containing the molten metal thereby providing a return path for the eddy currents induced in the metal sheet by the AC coil generated magnetic flux. Variation in the geometry of the conducting shield allows the magnetic flux between the metal sheet and the conducting shield to be varied and the thickness in surface quality of the metal sheet to be controlled. Side guards provide lateral containment for the molten metal sheet and stabilize and shape the magnetic field while a leader sheet having electromagnetic characteristics similar to those of the metal sheet is used to start the casting process and precedes the molten metal sheet through the magnet and forms a continuous sheet therewith. The magnet may be either U-shaped with a single racetrack coil or may be rectangular with a pair of facing bedstead coils.

  4. Horizontal electromagnetic casting of thin metal sheets

    DOEpatents

    Hull, John R.; Lari, Robert J.; Praeg, Walter F.; Turner, Larry R.

    1987-01-01

    Thin metal sheets are cast by magnetically suspending molten metal deposited within a ferromagnetic yoke and between AC conducting coils and linearly displacing the magnetically levitated liquid metal while it is being cooled to form a solid metal sheet. Magnetic flux increases as the molten metal sheet moves downward and decreases as the molten metal sheet moves upward to stabilize the sheet and maintain it in equilibrium as it is linearly displaced and solidified by cooling gases. A conducting shield is electrically coupled to the molten metal sheet by means of either metal sheet engaging rollers or brushes on the solidified metal, and by means of an electrode in the vessel containing the molten metal thereby providing a return path for the eddy currents induced in the metal sheet by the AC coil generated magnetic flux. Variation in the geometry of the conducting shield allows the magnetic flux between the metal sheet and the conducting shield to be varied and the thickness in surface quality of the metal sheet to be controlled. Side guards provide lateral containment for the molten metal sheet and stabilize and shape the magnetic field while a leader sheet having electromagnetic characteristics similar to those of the metal sheet is used to start the casting process and precedes the molten metal sheet through the magnet and forms a continuous sheet therewith. The magnet may be either U-shaped with a single racetrack coil or may be rectangular with a pair of facing bedstead coils.

  5. On the modelling of complex kinematic hardening and nonquadratic anisotropic yield criteria at finite strains: application to sheet metal forming

    NASA Astrophysics Data System (ADS)

    Grilo, Tiago J.; Vladimirov, Ivaylo N.; Valente, Robertt A. F.; Reese, Stefanie

    2016-06-01

    In the present paper, a finite strain model for complex combined isotropic-kinematic hardening is presented. It accounts for finite elastic and finite plastic strains and is suitable for any anisotropic yield criterion. In order to model complex cyclic hardening phenomena, the kinematic hardening is described by several back stress components. To that end, a new procedure is proposed in which several multiplicative decompositions of the plastic part of the deformation gradient are considered. The formulation incorporates a completely general format of the yield function, which means that any yield function can by employed by following a procedure that ensures the principle of material frame indifference. The constitutive equations are derived in a thermodynamically consistent way and numerically integrated by means of a backward-Euler algorithm based on the exponential map. The performance of the constitutive model is assessed via numerical simulations of industry-relevant sheet metal forming processes (U-channel forming and draw/re-draw of a panel benchmarks), the results of which are compared to experimental data. The comparison between numerical and experimental results shows that the use of multiple back stress components is very advantageous in the description of springback. This holds in particular if one carries out a comparison with the results of using only one component. Moreover, the numerically obtained results are in excellent agreement with the experimental data.

  6. Metals Fact Sheet: Yttrium

    SciTech Connect

    1992-09-01

    Yttrium is a metallic element usually included among the rare earth metals, which it resembles chemically and with which it usually occurs in minerals. Yttrium was named after the village of Ytterby in Sweden---the element was discovered in a quarry near the village. This article discusses sources of the element, the world market for the element, and various applications of the material.

  7. Metals fact sheet: Ruthenium

    SciTech Connect

    1996-06-01

    Ruthenium, named after Ruthenia, a province in Western Russia, was discovered in 1827 by Osann in placer ores from Russia`s Ural mountains. A minor platinum group metal (PGM), Ruthenium was the last of the PGMs to be isolated. In 1844, Klaus prepared the first 6 grams of pure ruthenium metal.

  8. Metals fact sheet - uranium

    SciTech Connect

    1996-04-01

    About 147 million pounds of this radioactive element are consumed annually by the worldwide nuclear power and weapons industries, as well as in the manufacture of ceramics and metal products. The heaviest naturally occurring element, uranium is typically found in intrusive granites, igneous and metamorphic veins, tabular sedimentary deposits, and unconformity-related structures. This article discusses the geology, exploitation, market, and applications of uranium and uranium ores.

  9. Sheet Metal Worker: A Training Profile.

    ERIC Educational Resources Information Center

    Ontario Ministry of Skills Development, Toronto.

    This training profile is intended for use by program developers and trainers in the development of training courses and programs for sheet metal workers. It contains 17 modules: safety for sheet metal worker; tools and machinery; materials and gauges; drafting and shop drawing; pattern development; methods of joining sheet metal; shearing and…

  10. Air Guide for Sheet-Metal Grinder

    NASA Technical Reports Server (NTRS)

    Heermann, T.

    1984-01-01

    Tool attachment reduces heat distortion of sheet. Air-guide attachment directs air from grinder motor to grinding wheel and metal sheet being ground. Cooling air reduces thermal distortion of workpiece due to localized frictional heating. Particularly useful when grinding sheet metal.

  11. Fact Sheet: Range Complex

    NASA Technical Reports Server (NTRS)

    Cornelson, C.; Fretter, E.

    2004-01-01

    NASA Ames has a long tradition in leadership with the use of ballistic ranges and shock tubes for the purpose of studying the physics and phenomena associated with hypervelocity flight. Cutting-edge areas of research run the gamut from aerodynamics, to impact physics, to flow-field structure and chemistry. This legacy of testing began in the NACA era of the 1940's with the Supersonic Free Flight Tunnel, and evolved dramatically up through the late 1950s with the pioneering work in the Ames Hypersonic Ballistic Range. The tradition continued in the mid-60s with the commissioning of the three newest facilities: the Ames Vertical Gun Range (AVGR) in 1964, the Hypervelocity Free Flight Facility (HFFF) in 1965 and the Electric Arc Shock Tube (EAST) in 1966. Today the Range Complex continues to provide unique and critical testing in support of the Nation's programs for planetary geology and geophysics; exobiology; solar system origins; earth atmospheric entry, planetary entry, and aerobraking vehicles; and various configurations for supersonic and hypersonic aircraft.

  12. Aircraft Sheet Metal Practices, Blueprint Reading, Sheet Metal Forming and Heat Treating; Sheet Metal Work 2: 9855.04.

    ERIC Educational Resources Information Center

    Dade County Public Schools, Miami, FL.

    This course is designed to familiarize vocational students with construction in sheet metal layout. The document outlines goals, specific block objectives, layout practices, blueprint reading, sheet metal forming (by hand and by machine), and heat treatment of metals, and includes posttest samples. Layout techniques and air foil developing are…

  13. 6. DETAIL VIEW OF SHEET METAL CORNICE AT SOUTHEAST CORNER ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    6. DETAIL VIEW OF SHEET METAL CORNICE AT SOUTHEAST CORNER OF MILL HOUSE, LOOKING NORTHWEST - Sperry Corn Elevator Complex, Weber Avenue (North side), West of Edison Street, Stockton, San Joaquin County, CA

  14. Triggers for β-sheet formation at the hydrophobic-hydrophilic interface: high concentration, in-plane orientational order, and metal ion complexation.

    PubMed

    Hoernke, Maria; Falenski, Jessica A; Schwieger, Christian; Koksch, Beate; Brezesinski, Gerald

    2011-12-06

    Amyloid formation plays a causative role in neurodegenerative diseases such as Alzheimer's disease or Parkinson's disease. Soluble peptides form β-sheets that subsequently rearrange into fibrils and deposit as amyloid plaques. Many parameters trigger and influence the onset of the β-sheet formation. Early stages are recently discussed to be cell-toxic. Aiming at understanding various triggers such as interactions with hydrophobic-hydrophilic interfaces and metal ion complexation and their interplay, we investigated a set of model peptides at the air-water interface. We are using a general approach to a variety of diseases such as Alzheimer's disease, Parkinson's disease, and type II diabetes that are connected to amyloid formation. Surface sensitive techniques combined with film balance measurements have been used to assess the conformation of the peptides and their orientation at the air-water interface (IR reflection-absorption spectroscopy). Additionally, the structures of the peptide layers were characterized by grazing incidence X-ray diffraction and X-ray reflectivity. The peptides adsorb to the air-water interface and immediately adopt an α-helical conformation. This helical intermediate transforms into β-sheets upon further triggering. The factors that result in β-sheet formation are dependent on the peptide sequence. In general, the interface has the strongest effect on peptide conformation compared to high concentrations or metal ions. Metal ions are able to prevent aggregation in bulk but not at the interface. At the interface, metal ion complexation has only minor effects on the peptide secondary structure, influencing the in-plane structure that is formed in two dimensions. At the air-water interface, increased concentrations or a parallel arrangement of the α-helical intermediates are the most effective triggers. This study reveals the role of various triggers for β-sheet formation and their complex interplay. Our main finding is that the

  15. Synthesis of Metal Phthalocyanine Sheet Polymers

    NASA Technical Reports Server (NTRS)

    Achar, B. N.; Fohlen, G. M.; Parker, J. A.

    1986-01-01

    New method for synthesizing metal phthalocyanine tetracarboxylic acids (MPTCA's) yields high purity end product. In addition, high-purity metal phthalocyanine sheet polymers synthesized from compounds. Monomer formed into sheet polymer by heating. Units of polymer linked in manner similar to phenyl-group linkages in biphenyl: Conjugation extends throughout macromolecule, thereby increasing delocalization of TT-electrons. Increases conductivity and thermal stability of polymer.

  16. Aircraft Sheet Metal Practices; Sheet Metal Work 2: 9855.01.

    ERIC Educational Resources Information Center

    Dade County Public Schools, Miami, FL.

    The course outline will serve as a guide to the 11th grade student interested in sheet metal occupations. Requiring 135 clock hours, the basic course covers orientation and techniques in aircraft sheet metal. Emphasis will be placed on the proper use of tools and machines, safety, fabrication methods, aircraft materials, basic layout, and special…

  17. Interior view of the Sheet Metal Shop showing the roof ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    Interior view of the Sheet Metal Shop showing the roof trusses and corrugated metal roof covering, view facing northwest - Kahului Cannery, Plant No. 28, Boiler House, Sheet Metal and Electrical Shops, 120 Kane Street, Kahului, Maui County, HI

  18. Molding cork sheets to complex shapes

    NASA Technical Reports Server (NTRS)

    Sharpe, M. H.; Simpson, W. G.; Walker, H. M.

    1977-01-01

    Partially cured cork sheet is easily formed to complex shapes and then final-cured. Temperature and pressure levels required for process depend upon resin system used and final density and strength desired. Sheet can be bonded to surface during final cure, or can be first-formed in mold and bonded to surface in separate step.

  19. Metals Fact Sheet: Gadolinium GD

    SciTech Connect

    1992-10-01

    Gadolinium is a silvery-white, malleable, ductile metallic element used to improve the high-temperature characteristics of iron, chromium, and related metallic alloys. It was named after the French chemist, Gadolin, discoverer of yttrium. This article discusses sources of the element, the world supply and demand, and also a number of applications. With the largest thermal neutron absorption cross section of any element, one of these applications is as a burnable poison in reactors and as neutron absorbers in other nuclear devices.

  20. Metals fact sheet--cesium

    SciTech Connect

    1997-03-01

    Cesium, the most alkaline and electropositive metal, is used by several industries for a variety of applications, including chemical catalysis, biomedical, photoelectrical, and glass manufacturing. While the traditional market for cesium has remained small, potential growth areas exist in the chemical catalysis and the oil and gas industry.

  1. Structures of Thin Sheet Metal, Their Design and Construction

    NASA Technical Reports Server (NTRS)

    Wagner, Herbert

    1928-01-01

    This report presents a brief survey of the uses of sheet-metal coverings in conjunction with the inner structure. A method of construction is presented as well as a discussion on the strength of sheet metal.

  2. Electromagnetic augmentation for casting of thin metal sheets

    DOEpatents

    Hull, J.R.

    1987-10-28

    Thin metal sheets are cast by magnetically levitating molten metal deposited in a model within a ferromagnetic yoke and between AC conducting coils and linearly displacing the magnetically levitated liquid metal while it is being cooled by the water-cooled walls of the mold to form a solid metal sheet. A conducting shield is electrically coupled to the molten metal sheet to provide a return path for eddy currents induced in the metal sheet by the current in the AC conducting coils. In another embodiment, a DC conducting coil is coupled to the metal sheet for providing a direct current therein which interacts with the magnetic field to levitate the moving metal sheet. Levitation of the metal sheet in both molten and solid forms reduces its contact pressure with the mold walls while maintaining sufficient engagement therebetween to permit efficient conductive cooling by the mold through which a coolant fluid may be circulated. 8 figs.

  3. Introduction to Sheet Metal. Instructor Edition. Introduction to Construction Series.

    ERIC Educational Resources Information Center

    Oklahoma State Dept. of Vocational and Technical Education, Stillwater. Curriculum and Instructional Materials Center.

    This instructor's guide contains the materials required to teach a competency-based introductory course in sheet metal work to students who have chosen to explore careers in construction. The following topics are covered in the course's three instructional units: sheet metal materials, sheet metal tools, and applied skills. Each unit contains some…

  4. Electromagnetic augmentation for casting of thin metal sheets

    DOEpatents

    Hull, John R.

    1989-01-01

    Thin metal sheets are cast by magnetically levitating molten metal deposited in a mold within a ferromagnetic yoke and between AC conducting coils and linearly displacing the magnetically levitated liquid metal while it is being cooled by the water-cooled walls of the mold to form a solid metal sheet. A conducting shield is electrically coupled to the molten metal sheet to provide a return path for eddy currents induced in the metal sheet by the current in the AC conducting coils. In another embodiment, a DC conducting coil is coupled to the metal sheet for providing a direct current therein which interacts with the magnetic field to levitate the moving metal sheet. Levitation of the metal sheet in both molten and solid forms reduces its contact pressure with the mold walls while maintaining sufficient engagement therebetween to permit efficient conductive cooling by the mold through which a coolant fluid may be circulated. The magnetic fields associated with the currents in the aforementioned coils levitate the molten metal sheet while the mold provides for its lateral and vertical confinement. A leader sheet having electromagnetic characteristics similar to those of the molten metal sheet is used to start the casing process and precedes the molten metal sheet through the yoke/coil arrangement and mold and forms a continuous sheet therewith. The yoke/coil arrangement may be either U-shaped with a single racetrack coil or may be rectangular with a pair of spaced, facing bedstead coils.

  5. Mississippi Curriculum Framework for Sheet Metal Programs (Program CIP: 48.0506--Sheet Metal Worker). Postsecondary Programs.

    ERIC Educational Resources Information Center

    Mississippi Research and Curriculum Unit for Vocational and Technical Education, State College.

    This document provides the framework for a postsecondary sheet metal program of instruction. A foreword provides guidelines that were used in developing the program and should be considered in compiling and revising course syllabi and daily lesson plans at the local level. A description of the sheet metal programs (building trades sheet metal work…

  6. Face split interpretations in sheet metal design

    NASA Astrophysics Data System (ADS)

    Vitalii, Vorkov; Dewil, Reginald; Mannaerts, Jef; Vandepitte, Dirk; Duflou, Joost R.

    2016-10-01

    Most of the modern CAD systems have capabilities to work with sheet metal parts. However, the functionality of these modules is limited to modelling, unfolding and delivering project documentation. In some cases the proposed design cannot be manufactured without splitting one or more faces of the part. In the current work, the graph representation of sheet metal parts and corresponding flat patterns are discussed. A splitting procedure is introduced which keeps all existing connections between faces intact. In addition, three interpretations for splitting are presented and recommendations for possible usage are given. The splitting procedure is found to be a convenient option to create feasible flat patterns. In addition, the different splitting interpretations present more flexibility to the designer.

  7. Fabricating Slotted-Waveguide Arrays From Sheet Metal

    NASA Technical Reports Server (NTRS)

    Brown, W. C.

    1983-01-01

    Low-cost lightweight waveguides formed from rolls of aluminum. Array formed from sheared, punched, and bent aluminum sheets. Sheets alined with punched jig holes and joined by laser-beam or resistance spot welding. Process permits use of thin metal to reduce raw material costs and mass. Also holds closer tolerances than usually attained in sheet-metal work.

  8. Career Preparation Program Curriculum Guide for: Metal Fabrication, Sheet Metal.

    ERIC Educational Resources Information Center

    British Columbia Dept. of Education, Victoria. Curriculum Development Branch.

    This curriculum outline provides secondary and postsecondary instructors with detailed information on student learning outcomes for completion of the sheet metal fabrication program requirements. A program overview discusses the aims of education; secondary school philosophy; and career preparation programs and their goals, organization, and…

  9. 46. NORTH THROUGH SHEET METAL AND ASSEMBLY AREA IN SOUTHWESTERN ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    46. NORTH THROUGH SHEET METAL AND ASSEMBLY AREA IN SOUTHWESTERN QUADRANT OF FACTORY AS SEEN FROM DOORWAY IN SOUTH FRONT WALL. ALONG WEST INTERIOR WALL ARE SHELVES BEARING WATER PUMPS, PARTS FOR PUMPS AND WATER SUPPLY EQUIPMENT, AND NEW OLD STOCK MERCHANDISE. IN FRONT OF THE WALL ARE THE CIRCA 1900 SHEET METAL SHEAR AND CIRCA 1900 SHEET METAL BRAKE. AT THE RIGHT SIDE OF THE IMAGE ALONGSIDE VERTICAL CEILING SUPPORTS IS METAL-COVERED BENCH FOR SHEET METAL WORK. - Kregel Windmill Company Factory, 1416 Central Avenue, Nebraska City, Otoe County, NE

  10. Oligocyclopentadienyl transition metal complexes

    SciTech Connect

    de Azevedo, Cristina G.; Vollhardt, K. Peter C.

    2002-01-18

    Synthesis, characterization, and reactivity studies of oligocyclopentadienyl transition metal complexes, namely those of fulvalene, tercyclopentadienyl, quatercyclopentadienyl, and pentacyclopentadienyl(cyclopentadienyl) are the subject of this account. Thermal-, photo-, and redox chemistries of homo- and heteropolynuclear complexes are described.

  11. Thin, porous metal sheets and methods for making the same

    SciTech Connect

    Liu, Wei; Li, Xiaohong Shari; Canfield, Nathan L.

    2015-07-14

    Thin, porous metal sheets and methods for forming them are presented to enable a variety of applications and devices. The thin, porous metal sheets are less than or equal to approximately 200 .mu.m thick, have a porosity between 25% and 75% by volume, and have pores with an average diameter less than or equal to approximately 2 .mu.m. The thin, porous metal sheets can be fabricated by preparing a slurry having between 10 and 50 wt % solvent and between 20 and 80 wt % powder of a metal precursor. The average particle size in the metal precursor powder should be between 100 nm and 5 .mu.m.

  12. Electrical upsetting of metal sheet forms weld edge

    NASA Technical Reports Server (NTRS)

    Scherba, E. S.

    1966-01-01

    Electric gathering of sheet stock edges forms metal sheets in the shape of gore sections with heavier edge areas that can be welded without loss of strength. The edges are gathered by progressive resistance heating and upsetting, and are formed automatically. This process avoids disturbance of the metals internal structure.

  13. Precision Sheet Metal. Progress Record and Theory Outline.

    ERIC Educational Resources Information Center

    Connecticut State Dept. of Education, Hartford. Div. of Vocational-Technical Schools.

    This combination progress record and course outline is designed for use by individuals teaching a course in precision sheet metal. Included among the topics addressed in the course are the following: employment opportunities in metalworking, measurement and layout, orthographic projection, precision sheet metal drafting, simple layout, hand tools,…

  14. 44. SOUTHWEST TO CIRCA 1900 SHEET METAL BRAKE, THE MACHINE ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    44. SOUTHWEST TO CIRCA 1900 SHEET METAL BRAKE, THE MACHINE USED TO BEND SHEET METAL TO EXACT ANGLES AS IN STEEL WATER TANK MANUFACTURE. IN THE BACKGROUND IS THE INTERIOR WEST WALL OF THE FACTORY, ITS SHELVES BEARING WATER PUMPS, PARTS FOR PUMPS AND WATER SUPPLY EQUIPMENT, AND NEW OLD STOCK MERCHANDISE. - Kregel Windmill Company Factory, 1416 Central Avenue, Nebraska City, Otoe County, NE

  15. 43. WEST TO DETAIL OF WHEELED SHEET METAL WORK STATION ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    43. WEST TO DETAIL OF WHEELED SHEET METAL WORK STATION BEARING ON LEFT CIRCA 1900 ROLLS FOR BENDING STEEL WINDMILL BLADES TO PROPER CURVATURE AND ON RIGHT CIRCA 1900 BEADING MACHINE FOR ADDING STIFFENING CREASES TO THE EDGES OF SHEET METAL PARTS SUCH AS BLADES. - Kregel Windmill Company Factory, 1416 Central Avenue, Nebraska City, Otoe County, NE

  16. 45. WEST TO CIRCA 1900 SHEET METAL SHEAR, THE MACHINE ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    45. WEST TO CIRCA 1900 SHEET METAL SHEAR, THE MACHINE USED TO CUT SHEET METAL USED IN WINDMILLS AND WATER TANKS. IN THE BACKGROUND IS THE INTERIOR WEST WALL OF THE FACTORY, ITS SHELVES BEARING WATER PUMPS, PARTS FOR PUMPS AND WATER SUPPLY EQUIPMENT, AND NEW OLD STOCK MERCHANDISE. - Kregel Windmill Company Factory, 1416 Central Avenue, Nebraska City, Otoe County, NE

  17. Overview of Boiler House and Sheet Metal and Electrical Shops ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    Overview of Boiler House and Sheet Metal and Electrical Shops Building (center - with single large chimney), note the monitor on the original section of the Boiler House Building, view facing north - Kahului Cannery, Plant No. 28, Boiler House, Sheet Metal and Electrical Shops, 120 Kane Street, Kahului, Maui County, HI

  18. Laser-assisted sheet metal working in series production

    NASA Astrophysics Data System (ADS)

    Brecher, Christian; Emonts, Michael; Eckert, Markus

    2013-02-01

    Based on the demand for a responsible use of natural resources and energy the need for lightweight materials is increasing. The most common materials for lightweight production are high and highest strength steel. These materials are difficult to machine using conventional sheet metal working processes because the high strength leads to a limited formability and high tool wear. The Fraunhofer IPT developed the laser-assisted sheet metal working. Selective laser based heating of the part directly before machining softens the material locally. Thus the quality of the following cut can be increased, for example for shearing 1.4310 the clear cut surface ratio can be increased from 20% up to 100% using a shearing gap of 10% of the sheet thickness. Because of the softening of the material and thus the increased formability, parts with a higher complexity can be produced. For example 1.4310 can be bent laser-assisted with a radius of 0.25 mm instead of 2-3 mm using the conventional process. For the first time spring steel can be embossed with conventional tools up to 50% of the sheet thickness. For the implementation in series production a modular system upgrade "hy-PRESS" has been developed to include laser and scanner technology into existing presses. For decoupling the sensitive optical elements of the machine vibrations an active-passive damping system has been developed. The combination of this new hybrid process and the system technology allows to produce parts of high strength steel with a high complexity and quality.

  19. Sheet metal forming optimization by using surrogate modeling techniques

    NASA Astrophysics Data System (ADS)

    Wang, Hu; Ye, Fan; Chen, Lei; Li, Enying

    2017-01-01

    Surrogate assisted optimization has been widely applied in sheet metal forming design due to its efficiency. Therefore, to improve the efficiency of design and reduce the product development cycle, it is important for scholars and engineers to have some insight into the performance of each surrogate assisted optimization method and make them more flexible practically. For this purpose, the state-of-the-art surrogate assisted optimizations are investigated. Furthermore, in view of the bottleneck and development of the surrogate assisted optimization and sheet metal forming design, some important issues on the surrogate assisted optimization in support of the sheet metal forming design are analyzed and discussed, involving the description of the sheet metal forming design, off-line and online sampling strategies, space mapping algorithm, high dimensional problems, robust design, some challenges and potential feasible methods. Generally, this paper provides insightful observations into the performance and potential development of these methods in sheet metal forming design.

  20. Modeling of Sandwich Sheets with Metallic Foam

    SciTech Connect

    Mata, H.; Jorge, R. Natal; Fernandes, A. A.; Parente, M. P. L.; Santos, A.; Valente, R. A. F.

    2011-08-22

    World-wide vehicles safety experts agree that significant further reductions in fatalities and injuries can be achieved as a result of the use of new lightweight and energy absorbing materials. On this work, the authors present the development and evaluation of an innovative system able to perform reliable panels of sandwich sheets with metallic foam cores for industrial applications. The mathematical model used to describe the behavior of sandwich shells with metal cores foam is presented and some numerical examples are presented. In order to validate those results mechanical experiments are carried out. Using the crushable foam constitutive model, available on ABAQUS, a set of different mechanical tests were simulated. There are two variants of this model available on ABAQUS: the volumetric hardening model and the isotropic hardening model. As a first approximation we chose the isotropic hardening variant. The isotropic hardening model available uses a yield surface that is an ellipse centered at the origin in the p-q stress plane. Based on this constitutive model for the foam, numerical simulations of the tensile and bulge test will be conducted. The numerical results will be validated using the data obtained from the experimental results.

  1. Method and apparatus for determining weldability of thin sheet metal

    DOEpatents

    Goodwin, Gene M.; Hudson, Joseph D.

    1988-01-01

    A fixture is provided for testing thin sheet metal specimens to evaluate hot-cracking sensitivity for determining metal weldability on a heat-to-heat basis or through varying welding parameters. A test specimen is stressed in a first direction with a load selectively adjustable over a wide range and then a weldment is passed along over the specimen in a direction transverse to the direction of strain to evaluate the hot-cracking characteristics of the sheet metal which are indicative of the weldability of the metal. The fixture provides evaluations of hot-cracking sensitivity for determining metal weldability in a highly reproducible manner with minimum human error.

  2. Variation simulation for compliant sheet metal assemblies with applications

    NASA Astrophysics Data System (ADS)

    Long, Yufeng

    Sheet metals are widely used in discrete products, such as automobiles, aircraft, furniture and electronics appliances, due to their good manufacturability and low cost. A typical automotive body assembly consists of more than 300 parts welded together in more than 200 assembly fixture stations. Such an assembly system is usually quite complex, and takes a long time to develop. As the automotive customer demands products of increasing quality in a shorter time, engineers in automotive industry turn to computer-aided engineering (CAE) tools for help. Computers are an invaluable resource for engineers, not only to simplify and automate the design process, but also to share design specifications with manufacturing groups so that production systems can be tooled up quickly and efficiently. Therefore, it is beneficial to develop computerized simulation and evaluation tools for development of automotive body assembly systems. It is a well-known fact that assembly architectures (joints, fixtures, and assembly lines) have a profound impact on dimensional quality of compliant sheet metal assemblies. To evaluate sheet metal assembly architectures, a special dimensional analysis tool need be developed for predicting dimensional variation of the assembly. Then, the corresponding systematic tools can be established to help engineers select the assembly architectures. In this dissertation, a unified variation model is developed to predict variation in compliant sheet metal assemblies by considering fixture-induced rigid-body motion, deformation and springback. Based on the unified variation model, variation propagation models in multiple assembly stations with various configurations are established. To evaluate the dimensional capability of assembly architectures, quantitative indices are proposed based on the sensitivity matrix, which are independent of the variation level of the process. Examples are given to demonstrate their applications in selecting robust assembly

  3. Working with Design: A Package for Sheet Metal

    ERIC Educational Resources Information Center

    Fiebich, Paul D.

    1974-01-01

    The author describes a design approach used to study sheet metal layout in junior high and high school mechanical drafting courses. Students observe packaging in stores, study package construction, and design and produce their own packages. (EA)

  4. Method and Apparatus for Die Forming Metal Sheets and Extrusions.

    DTIC Science & Technology

    of a variety of die blocks for introducing a variety of angled joggles in the metal sheets and extrusions. Relatively low melting temperature material is used for the castings. Keywords: Patents; Aircraft parts. (kt)

  5. Analytical study for deformability of laminated sheet metal

    PubMed Central

    Serror, Mohammed H.

    2012-01-01

    While a freestanding high-strength sheet metal subject to tension will rupture at a small strain, it is anticipated that lamination with a ductile sheet metal will retard this instability to an extent that depends on the relative thickness, the relative stiffness, and the hardening exponent of the ductile sheet. This paper presents an analytical study for the deformability of such laminate within the context of necking instability. Laminates of high-strength sheet metal and ductile low-strength sheet metal are studied assuming: (1) sheets are fully bonded; and (2) metals obey the power law material model. The effect of hardening exponent, volume fraction and relative stiffness of the ductile component has been studied. In addition, stability of both uniform and nonuniform deformations has been investigated under plane strain condition. The results have shown the retardation of the high-strength layer instability by lamination with the ductile layer. This has been achieved through controlling the aforementioned key parameters of the ductile component, while the laminate exhibits marked enhancement in strength–ductility combination that is essential for metal forming applications. PMID:25685405

  6. Numerical Tool Path Optimization for Conventional Sheet Metal Spinning Processes

    NASA Astrophysics Data System (ADS)

    Rentsch, Benedikt; Manopulo, Niko; Hora, Pavel

    2016-08-01

    To this day, conventional sheet metal spinning processes are designed with a very low degree of automation. They are usually executed by experienced personnel, who actively adjust the tool paths during production. The practically unlimited freedom in designing the tool paths enables the efficient manufacturing of complex geometries on one hand, but is challenging to translate into a standardized procedure on the other. The present study aims to propose a systematic methodology, based on a 3D FEM model combined with a numerical optimization strategy, in order to design tool paths. The accurate numerical modelling of the spinning process is firstly discussed, followed by an analysis of appropriate objective functions and constraints required to obtain a failure free tool path design.

  7. Additive Manufacturing of Functional Elements on Sheet Metal

    NASA Astrophysics Data System (ADS)

    Schaub, Adam; Ahuja, Bhrigu; Butzhammer, Lorenz; Osterziel, Johannes; Schmidt, Michael; Merklein, Marion

    Laser Beam Melting (LBM) process with its advantages of high design flexibility and free form manufacturing methodology is often applied limitedly due to its low productivity and unsuitability for mass production compared to conventional manufacturing processes. In order to overcome these limitations, a hybrid manufacturing methodology is developed combining the additive manufacturing process of laser beam melting with sheet forming processes. With an interest towards aerospace and medical industry, the material in focus is Ti-6Al-4V. Although Ti-6Al-4V is a commercially established material and its application for LBM process has been extensively investigated, the combination of LBM of Ti-6Al-4V with sheet metal still needs to be researched. Process dynamics such as high temperature gradients and thermally induced stresses lead to complex stress states at the interaction zone between the sheet and LBM structure. Within the presented paper mechanical characterization of hybrid parts will be performed by shear testing. The association of shear strength with process parameters is further investigated by analyzing the internal structure of the hybrid geometry at varying energy inputs during the LBM process. In order to compare the hybrid manufacturing methodology with conventional fabrication, the conventional methodologies subtractive machining and state of the art Laser Beam Melting is evaluated within this work. These processes will be analyzed for their mechanical characteristics and productivity by determining the build time and raw material consumption for each case. The paper is concluded by presenting the characteristics of the hybrid manufacturing methodology compared to alternative manufacturing technologies.

  8. A New Sheet Metal Forming System Based on Incremental Punching

    NASA Astrophysics Data System (ADS)

    Luo, Yuanxin

    conducted by the mean of computer simulation in consideration of applying a large impulsive force. This study validates the machine stability and accuracy. One of the keys to successful application of sheet metal forming is to be able to predict the deformation and the strain/stress of the part incurred during the forming process. Because of the complexity of the ISMF process, it is not possible to derive an analytical method. The alternative is to use Finite Element Analysis (FEA). However, based on our experience, it takes about one week to solve a simple case. A mechanics model is therefore developed. It consists of two steps. The first step is to computer the final shape: the initial geometric surface is obtained using the punch positions; then using the minimum energy principle, the virtual forces drive the nodes of geometric surface to their lowest energy positions, which gives the final shape of the forming part. The second step is to predict the strain and stress distributions. This is done using the inverse Finite Element Modeling (FEM). An in-house computer software is developed using MATLABRTM. In order to verify the new mechanics model, numerical and experimental studies are conducted using the new incremental punching system. The final shape and thickness distributions of parts are compared to verify the mechanics model. It is found that the model prediction fits the experiment result well. Forming parameters are also investigated. To evaluate the capability of the presented ISMF process, the formability is studied by the means of theory and experiment. A modified M-K model is proposed for predicting the forming limit of the formed part which is undergoing a very complicated strain path. The maximum forming angle is also investigated by experiments.

  9. Selenophene transition metal complexes

    SciTech Connect

    White, Carter James

    1994-07-27

    This research shows that selenophene transition metal complexes have a chemistry that is similar to their thiophene analogs. Selenophene coordination has been demonstrated and confirmed by molecular structure in both the η5- and the η1(Se)-coordination modes. The reaction chemistry of selenophene complexes closely resembles that of the analogous thiophene complexes. One major difference, however, is that selenophene is a better donor ligand than thiophene making the selenophene complexes more stable than the corresponding thiophene complexes. The 77Se NMR chemical shift values for selenophene complexes fall within distinct regions primarily depending on the coordination mode of the selenophene ligand. In the final paper, the C-H bond activation of η1(S)-bound thiophenes, η1(S)-benzothiophene and η1(Se)-bound selenophenes has been demonstrated. The deprotonation and rearrangement of the η1(E)-bound ligand to the carbon bound L-yl complex readily occurs in the presence of base. Reprotonation with a strong acid gives a carbene complex that is unreactive towards nucleophilic attack at the carbene carbon and is stable towards exposure to air. The molecular structure of [Cp(NO)(PPh3)Re(2-benzothioenylcarbene)]O3SCF3 was determined and contains a Re-C bond with substantial double bond character. Methyl substitution for the thienylcarbene or selenylcarbene gives a carbene that rearranges thermally to give back the η1(E)-bound complex. Based on these model reactions, a new mechanism for the H/D exchange of thiophene over the hydrodesulfurization catalyst has been proposed.

  10. Including die and press deformations in sheet metal forming simulations

    NASA Astrophysics Data System (ADS)

    Pilthammar, Johan; Sigvant, Mats; Kao-Walter, Sharon

    2016-08-01

    Structural analysis, in Abaqus, of a stamping die and subsequent morphing of the tool surfaces in AutoForm were performed to improve a sheet metal forming simulation. First, the tool surfaces of the XC90 rear door inner were scanned. They were not matching when the die was unloaded and could therefore not give any satisfying results in sheet metal forming simulations. Scanned surface geometries were then added to a structural FE-model of the complete stamping die and some influential parts of the production press. The structural FE- model was analysed with Abaqus to obtain the structural deformations of the die. The calculated surface shapes were then transferred to AutoForm where a forming simulation was performed. Results from the different sheet metal forming simulations were compared to measured draw in curves and showed a substantial increase in accuracy and ability to analyse dies in running production when the morphed surfaces were used.

  11. Formability Evaluation of Sheet Metals Based on Global Strain Distribution

    NASA Astrophysics Data System (ADS)

    Zhang, Ling; Lin, Jianping; Min, Junying; Ye, You; Kang, Liugen

    2016-06-01

    According to the conventional methods for formability evaluation, e.g., forming limit curve (FLC), limit dome height, and total elongation, inconsistent results are observed when comparing the formability of four advanced high-strength steels (AHSS) with an ultimate tensile strength grade of 1000 MPa. The strain distribution analysis with the aid of digital image correlation technique shows that different uniform deformation capabilities of sheet metals under the same loading conditions are responsible for this inconsistency. In addition, metallurgical analysis suggests that inhomogeneous microstructure distribution and phase transformation during deformation in some materials play important roles in the uniform deformation capability of sheet metal. Limit strains on the commonly used FLC only relate to the major and minor strains of local deforming elements associated with the onset of necking. However, the formability of a sheet metal component is determined by the strain magnitudes of all deforming elements involved during the forming process. Hence, the formability evaluation of sheet metals from a global aspect is more applicable for practical engineering. A new method based on two indices (i.e., which represent global formability and uniform deformation capability, respectively) is proposed to evaluate the formability of sheet metals based on global strain distribution. The formability and evolution of deformation uniformity of the investigated AHSS at different stress states are studied with this new method. Compared with other formability evaluation methods, the new method is demonstrated to be more appropriate for practical engineering, and it is applicable to both in-plane and out-of-plane deformation. Additionally, the global formability of sheet metals can be more comprehensively understood with this new method.

  12. Asbestos disease in sheet metal workers: proportional mortality update

    SciTech Connect

    Michaels, D.; Zoloth, S.

    1988-01-01

    This paper, updating the findings of an earlier study, provides additional evidence that sheet metal workers in the construction trades are at increased risk for asbestos-related disease. A proportional analysis of cause of death among 331 New York sheet metal workers found a significantly elevated PMR for lung cancer (PMR = 186). In addition, there were six deaths attributable to mesothelioma (three classified as lung cancer deaths) and three death certificates mentioned asbestosis or pulmonary fibrosis, although none of these three deaths were attributed to these diseases.

  13. Robust Design of Sheet Metal Forming Process Based on Kriging Metamodel

    NASA Astrophysics Data System (ADS)

    Xie, Yanmin

    2011-08-01

    Nowadays, sheet metal forming processes design is not a trivial task due to the complex issues to be taken into account (conflicting design goals, complex shapes forming and so on). Optimization methods have also been widely applied in sheet metal forming. Therefore, proper design methods to reduce time and costs have to be developed mostly based on computer aided procedures. At the same time, the existence of variations during manufacturing processes significantly may influence final product quality, rendering non-robust optimal solutions. In this paper, a small size of design of experiments is conducted to investigate how a stochastic behavior of noise factors affects drawing quality. The finite element software (LS_DYNA) is used to simulate the complex sheet metal stamping processes. The Kriging metamodel is adopted to map the relation between input process parameters and part quality. Robust design models for sheet metal forming process integrate adaptive importance sampling with Kriging model, in order to minimize impact of the variations and achieve reliable process parameters. In the adaptive sample, an improved criterion is used to provide direction in which additional training samples can be added to better the Kriging model. Nonlinear functions as test functions and a square stamping example (NUMISHEET'93) are employed to verify the proposed method. Final results indicate application feasibility of the aforesaid method proposed for multi-response robust design.

  14. Blueprint Reading for Sheet Metal Workers. Training Guide.

    ERIC Educational Resources Information Center

    Anoka-Hennepin Technical Coll., Minneapolis, MN.

    This training guide, developed during a project to retrain defense industry workers at risk of job loss or dislocation because of conversion of the defense industry, is designed for a course in blueprint reading for sheet metal workers. The following are among the topics covered in the course: orthographic projection; isometric and oblique…

  15. 17. VIEW OF FORMING EQUIPMENT, DISCS CUT FROM METAL SHEETS ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    17. VIEW OF FORMING EQUIPMENT, DISCS CUT FROM METAL SHEETS WERE FORMED INTO SHAPES. (7/2/86) - Rocky Flats Plant, Uranium Rolling & Forming Operations, Southeast section of plant, southeast quadrant of intersection of Central Avenue & Eighth Street, Golden, Jefferson County, CO

  16. A Collaborative Design Curriculum for Reviving Sheet Metal Handicraft

    ERIC Educational Resources Information Center

    Chan, Patrick K. C.

    2015-01-01

    Galvanised sheet metal was a popular and important material for producing handmade home utensils in Hong Kong from the 1930s onwards. It was gradually replaced by new materials like stainless steel and plastic because similar goods made with these are cheaper, more standardised, more durable and of much better quality. The handicrafts behind sheet…

  17. Formability of porous tantalum sheet-metal

    NASA Astrophysics Data System (ADS)

    Nebosky, Paul S.; Schmid, Steven R.; Pasang, Timotius

    2009-08-01

    Over the past ten years, a novel cellular solid, Trabecular Metal™, has been developed for use in the orthopaedics industry as an ingrowth scaffold. Manufactured using chemical vapour deposition (CVD) on top of a graphite foam substrate, this material has a regular matrix of interconnecting pores, high strength, and high porosity. Manufacturing difficulties encourage the application of bending, stamping and forming technologies to increase CVD reactor throughput and reduce material wastes. In this study, the bending and forming behaviour of Trabecular Metal™ was evaluated using a novel camera-based system for measuring surface strains, since the conventional approach of printing or etching gridded patterns was not feasible. A forming limit diagram was obtained using specially fabricated 1.65 mm thick sheets. A springback coefficient was measured and modeled using effective hexagonal cell arrangements.

  18. Anisotropy and Formability in Sheet Metal Forming

    SciTech Connect

    Houtte, P. van; Bael, A.; He, S. van

    2007-05-17

    Two types of anisotropy have been introduced in the Marciniak model for the prediction of forming limit diagrams (FLDs) of sheet material. One type is due to crystallographic texture, the other is due to dislocation substructure. First, an anisotropic plastic potential is derived from a measured crystallographic texture using a multilevel model. The yield locus can be derived from this plastic potential. In addition to this, a model is used to simulate microstructure-induced work hardening and softening. This model can take effects of strain path changes into account. Both the texture-based and microstructure-based anisotropic model are then implemented in the Marciniak model and used for FLD calculation. Examples of application are given for IOF steel and for aluminium alloys. Recent research has focused on the physical basis of the microstructure-induced work hardening and softening. The principles of this model will be elucidated.

  19. Bifurcation Instability of sheet metal during spring-back

    NASA Astrophysics Data System (ADS)

    Kim, Jong-Bong; Yang, Dong-Yol; Yoon, Jeong Whan

    2013-05-01

    In automotive and home appliance industries, there are many complex-shaped sheet metal components which need to be fabricated in multiple stamping operations. For example, the manufacturing of an outer case of washing machine consists of stamping followed by a bending operation. After the first stage of the stamping process, a large amount of spring-back takes place, and therefore, it is difficult to proceed to the next stage of the bending process. In the stamping process of that kind of sheet component with low geometric constraint, the forming area is large compared to the forming depth. Therefore, the formed part is in an unstable state and is less geometrically constrained, which causes a large amount of spring-back. To investigate this phenomenon, finite element analyses are carried out. During a spring-back analysis after forming, bifurcation takes place and the finite element solution procedure using the Newton-Raphson scheme becomes unstable. To get a stable post-bifurcation solution, a bifurcation algorithm is introduced at the bifurcation point. The deformed shapes obtained from finite element analyses are in good agreement with the experimental data. From this study, it is shown that the bifurcation behaviour enlarges the spring-back and the degree of dimensional error. To obtain additional possible post-bifurcation solutions, non-bifurcation analyses using initial guesses obtained in a modal analysis are carried. For the initial guesses, lowed four eigenmodes are utilized. Finally, the post-bifurcation behaviour and spring-back amount are investigated for various process parameters including the forming depth, punch width and corner radius.

  20. Knowledge Based Cloud FE Simulation of Sheet Metal Forming Processes.

    PubMed

    Zhou, Du; Yuan, Xi; Gao, Haoxiang; Wang, Ailing; Liu, Jun; El Fakir, Omer; Politis, Denis J; Wang, Liliang; Lin, Jianguo

    2016-12-13

    The use of Finite Element (FE) simulation software to adequately predict the outcome of sheet metal forming processes is crucial to enhancing the efficiency and lowering the development time of such processes, whilst reducing costs involved in trial-and-error prototyping. Recent focus on the substitution of steel components with aluminum alloy alternatives in the automotive and aerospace sectors has increased the need to simulate the forming behavior of such alloys for ever more complex component geometries. However these alloys, and in particular their high strength variants, exhibit limited formability at room temperature, and high temperature manufacturing technologies have been developed to form them. Consequently, advanced constitutive models are required to reflect the associated temperature and strain rate effects. Simulating such behavior is computationally very expensive using conventional FE simulation techniques. This paper presents a novel Knowledge Based Cloud FE (KBC-FE) simulation technique that combines advanced material and friction models with conventional FE simulations in an efficient manner thus enhancing the capability of commercial simulation software packages. The application of these methods is demonstrated through two example case studies, namely: the prediction of a material's forming limit under hot stamping conditions, and the tool life prediction under multi-cycle loading conditions.

  1. Knowledge Based Cloud FE Simulation of Sheet Metal Forming Processes

    PubMed Central

    Zhou, Du; Yuan, Xi; Gao, Haoxiang; Wang, Ailing; Liu, Jun; El Fakir, Omer; Politis, Denis J.; Wang, Liliang; Lin, Jianguo

    2016-01-01

    The use of Finite Element (FE) simulation software to adequately predict the outcome of sheet metal forming processes is crucial to enhancing the efficiency and lowering the development time of such processes, whilst reducing costs involved in trial-and-error prototyping. Recent focus on the substitution of steel components with aluminum alloy alternatives in the automotive and aerospace sectors has increased the need to simulate the forming behavior of such alloys for ever more complex component geometries. However these alloys, and in particular their high strength variants, exhibit limited formability at room temperature, and high temperature manufacturing technologies have been developed to form them. Consequently, advanced constitutive models are required to reflect the associated temperature and strain rate effects. Simulating such behavior is computationally very expensive using conventional FE simulation techniques. This paper presents a novel Knowledge Based Cloud FE (KBC-FE) simulation technique that combines advanced material and friction models with conventional FE simulations in an efficient manner thus enhancing the capability of commercial simulation software packages. The application of these methods is demonstrated through two example case studies, namely: the prediction of a material's forming limit under hot stamping conditions, and the tool life prediction under multi-cycle loading conditions. PMID:28060298

  2. How To Cut a Round and a Square Inside Opening in a Piece of Sheet Metal Using Aviation Snips. Sheet Metal 1-001. Lesson Plan No. 2.

    ERIC Educational Resources Information Center

    Shibayama, Guy T.

    As part of a 90-hour community college course in sheet metal working, this 50-minute lesson was designed to enable a student to: (1) identify and use right and left hand aviation snips; (2) cut out a 6-inch round opening in a piece of sheet metal using aviation snips; and (3) cut out a 6-by-6 inch square opening in a piece of sheet metal using…

  3. Method and apparatus for die forming metal sheets and extrusions

    NASA Astrophysics Data System (ADS)

    Darter, John L.

    1986-06-01

    The invention comprises an apparatus for die forming metal sheets and extrusions which utilizes die blocks of low melting temperature metallic material. The die blocks are formed in an adjustable mold which comprises a mold box, a pivotable dam within the mold box and blocking means for locking the pivotable dam member in a desired angular position. Once a desired die block angle is ascertained for a particular joggle, the pivotable member of the mold box is adjusted to produce the desired angle in the die casting made in the mold box.

  4. Warm Hydroforming of Lightweight Metal Sheets

    SciTech Connect

    Aginagalde, A.; Orus, A.; Esnaola, J. A.; Torca, I.; Galdos, L.; Garcia, C.

    2007-05-17

    Hydroforming is well known in steel applications for automotive industry, where complicated shapes can be get with high strength to weight ratios. Nevertheless, the poor formability of light alloys at room temperature has limited the application of hydroforming technology for aluminum and magnesium parts. Increasing the temperature of these materials allows substantially greater elongation without fracture. Warm forming strategy is applied in conventional processes, such as rolling and forging, in order to get complex shapes, but still rare in hydroforming technology. This is the technical base of this research project: the development of the hydroforming process at warm working temperatures. The main tasks of the initial phases of the research were the material characterization, and the heated fluid and tooling system design and set up for warm hydroforming of lightweight alloys. Once these goals were accomplished the present paper shows the obtained results. The uniaxial tensile deformation of 5754H111, 6082-T6, 6082-O and AZ31B at the temperature range of 25 deg. C - 250 deg. C is presented as the output of the material characterization task. Both the system features and the results obtained for a bulge test geometry carried out with a warm hydroforming system are also presented. The selected alloys show an improvement in formability at the studied temperature range under both uniaxial and biaxial state of stress.

  5. Electromagnetic confinement and movement of thin sheets of molten metal

    DOEpatents

    Lari, Robert J.; Praeg, Walter F.; Turner, Larry R.

    1990-01-01

    An apparatus capable of producing a combination of magnetic fields that can retain a metal in liquid form in a region having a smooth vertical boundary including a levitation magnet that produces low frequency magnetic field traveling waves to retain the metal and a stabilization magnet that produces a high frequency magnetic field to produce a smooth vertical boundary. As particularly adapted to the casting of solid metal sheets, a metal in liquid form can be continuously fed into one end of the confinement region produced by the levitation and stabilization magnets and removed in solid form from the other end of confinement region. An additional magnet may be included for support at the edges of the confinement region where eddy currents loop.

  6. Fact Sheets: Final Rules to Reduce Toxic Air Pollutants from Surface Coating of Metal Cans

    EPA Pesticide Factsheets

    This page contains the August 2003 final rule fact sheet and the December 2005 final rule fact sheet that contain information on the National Emission Standards for Hazardous Air Pollutants (NESHAP) for Surface Coating of Metal Cans.

  7. Stabilization of ultrafine metal nanocatalysts on thin carbon sheets

    NASA Astrophysics Data System (ADS)

    Liu, Xiaofang; Cui, Xinrui; Liu, Yiding; Yin, Yadong

    2015-10-01

    A novel strategy was proposed to anchor ultrafine metal nanoparticles (NPs) on thin carbon sheets for highly stable and efficient heterogeneous catalysts. In this facile approach, a dense monolayer of ultrafine AuNPs was sandwiched between a silica core and a resin shell, followed by carbonization of the shell at a high temperature and then selective removal of the silica core. The shrinkage of the shells during carbonization facilitates partial embedment of the AuNPs on the carbon shell surface and provides superior stability against particle sintering during high temperature/mechanical post-treatments and catalytic reactions. It was also found that diffusion of reactants to the surface of AuNPs could be maximized by reducing the thickness of the hollow shells or simply by cracking the shells into thin carbon sheets, both significantly benefiting the catalytic efficiency. The advantages of this ultra-stable architecture together with the densely dispersed catalytic sites were demonstrated by their high stability and superior catalytic activity in reducing hydrophilic 4-nitrophenol and hydrophobic nitrobenzene.A novel strategy was proposed to anchor ultrafine metal nanoparticles (NPs) on thin carbon sheets for highly stable and efficient heterogeneous catalysts. In this facile approach, a dense monolayer of ultrafine AuNPs was sandwiched between a silica core and a resin shell, followed by carbonization of the shell at a high temperature and then selective removal of the silica core. The shrinkage of the shells during carbonization facilitates partial embedment of the AuNPs on the carbon shell surface and provides superior stability against particle sintering during high temperature/mechanical post-treatments and catalytic reactions. It was also found that diffusion of reactants to the surface of AuNPs could be maximized by reducing the thickness of the hollow shells or simply by cracking the shells into thin carbon sheets, both significantly benefiting the

  8. RIGGERS LOFT/PAINT SHOP/SHEET METAL SHOP, VIEW TO SOUTHEAST. THE PAINT ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    RIGGERS LOFT/PAINT SHOP/SHEET METAL SHOP, VIEW TO SOUTHEAST. THE PAINT SHOP WAS LOCATED IN THE CLOSEST CORNER OF THE BUILDING. THE SHEET METAL SHOP WAS LOCATED IN THE CORNER OF THE BUILDING ON THE RIGHT. THE RIGGERS LOFT WAS LOCATED IN THE PORTION OF THE BUILDING OUT OF VIEW TO THE LEFT - Rosie the Riveter National Historical Park, Riggers Loft/Paint Shop/Sheet Metal Shop, 1322 Canal Boulevard, Richmond, Contra Costa County, CA

  9. Self-Pierce Riveting Through 3 Sheet Metal Combinations

    NASA Astrophysics Data System (ADS)

    Andersson, Roger; Jonason, Paul; Pettersson, Tommy

    2011-05-01

    One way to reduce the CO2 emissions in automotives is to reduce the weight of the Body-In-White. One easy to achieve the weight reduction is to replace steel sheet materials with Al alloys, which is 3 times lighter. One issue is the joining process, especially with combinations between steel grades and AL alloys. Example of combination of mixed material combinations (Al-steel) might be found in the door structure. The reason is because of the AL alloys worthier crash performance so the automotive manufacturer might want to use crash impact beams made by high strength steels in a AL intensive door structure. The joining process between aluminum and steel are problematic due it's not possible to use traditional spot-welding technologies due to the materials total difference in microstructure characteristics as well thermal properties. To overcome this issue then mechanical as well adhesion joining are frequently used. This paper describes a development process and subsequently analysis of a self-pierce rivet (SPR) process between 3 sheet metal combinations. The multi-material combinations in this study were a combination of ultra high strength steels sheets (DP1000) and a Al-alloy (AA 6014). The analysis of the SPR process, in sense of mechanical strengths, has been done by peel- and shear tests. To reduce the amount of future physical tests a virtual FE-model has been developed for the process. This FE model of the process has been subsequently used to analyze the mechanical strength during plastic deformation. By using inverse analysis a correct contact algorithm has been evaluated that would predict the binding force between the rivet and sheet under a deformation process. With this new virtual model it will not only possible to analyze and develop the SPR process but also to achieve the final strength of the joint.

  10. Self-Pierce Riveting Through 3 Sheet Metal Combinations

    SciTech Connect

    Andersson, Roger; Jonason, Paul; Pettersson, Tommy

    2011-05-04

    One way to reduce the CO{sub 2} emissions in automotives is to reduce the weight of the Body-In-White. One easy to achieve the weight reduction is to replace steel sheet materials with Al alloys, which is 3 times lighter. One issue is the joining process, especially with combinations between steel grades and AL alloys. Example of combination of mixed material combinations (Al-steel) might be found in the door structure. The reason is because of the AL alloys worthier crash performance so the automotive manufacturer might want to use crash impact beams made by high strength steels in a AL intensive door structure. The joining process between aluminum and steel are problematic due it's not possible to use traditional spot-welding technologies due to the materials total difference in microstructure characteristics as well thermal properties. To overcome this issue then mechanical as well adhesion joining are frequently used. This paper describes a development process and subsequently analysis of a self-pierce rivet (SPR) process between 3 sheet metal combinations. The multi-material combinations in this study were a combination of ultra high strength steels sheets (DP1000) and a Al-alloy (AA 6014). The analysis of the SPR process, in sense of mechanical strengths, has been done by peel- and shear tests. To reduce the amount of future physical tests a virtual FE-model has been developed for the process. This FE model of the process has been subsequently used to analyze the mechanical strength during plastic deformation. By using inverse analysis a correct contact algorithm has been evaluated that would predict the binding force between the rivet and sheet under a deformation process. With this new virtual model it will not only possible to analyze and develop the SPR process but also to achieve the final strength of the joint.

  11. Application of Six Sigma Robust Optimization in Sheet Metal Forming

    SciTech Connect

    Li, Y.Q.; Cui, Z.S.; Ruan, X.Y.; Zhang, D.J.

    2005-08-05

    Numerical simulation technology and optimization method have been applied in sheet metal forming process to improve design quality and shorten design cycle. While the existence of fluctuation in design variables or operation condition has great influence on the quality. In addition to that, iterative solution in numerical simulation and optimization usually take huge computational time or endure expensive experiment cost In order to eliminate effect of perturbations in design and improve design efficiency, a CAE-based six sigma robust design method is developed in this paper. In the six sigma procedure for sheet metal forming, statistical technology and dual response surface approximate model as well as algorithm of 'Design for Six Sigma (DFSS)' are integrated together to perform reliability optimization and robust improvement. A deep drawing process of a rectangular cup is taken as an example to illustrate the method. The optimization solutions show that the proposed optimization procedure not only improves significantly the reliability and robustness of the forming quality, but also increases optimization efficiency with approximate model.

  12. Formability models for warm sheet metal forming analysis

    NASA Astrophysics Data System (ADS)

    Jiang, Sen

    Several closed form models for the prediction of strain space sheet metal formability as a function of temperature and strain rate are proposed. The proposed models require only failure strain information from the uniaxial tension test at an elevated temperature setting and failure strain information from the traditionally defined strain space forming limit diagram at room temperature, thereby featuring the advantage of offering a full forming limit description without having to carry out expensive experimental studies for multiple modes of deformation under the elevated temperature. The Power law, Voce, and Johnson-Cook hardening models are considered along with the yield criterions of Hill's 48 and Logan-Hosford yield criteria. Acceptable correlations between the theory and experiment are reported for all the models under a plane strain condition. Among all the proposed models, the model featuring Johnson-Cook hardening model and Logan-Hosford yield behavior (LHJC model) was shown to best correlate with experiment. The sensitivity of the model with respect to various forming parameters is discussed. This work is significant to those aiming to incorporate closed-form formability models directly into numerical simulation programs for the purpose of design and analysis of products manufactured through the warm sheet metal forming process. An improvement based upon Swift's diffuse necking theory, is suggested in order to enhance the reliability of the model for biaxial stretch conditions. Theory relating to this improvement is provided in Appendix B.

  13. Phosphoroorganic Metal Complexes in Therapeutics.

    PubMed

    Demkowicz, Sebastian; Kozak, Witold; Daśko, Mateusz; Rachon, Janusz

    2016-01-01

    The present mini-review highlights recent developments on antitumor activity of metal-based therapeutics which have been a subject of researches for the last few decades. In 1965, Rosenberg found that during an electrolysis on platinum electrodes a complex of Pt is generated which inhibited to a great extent a binary fission in Escherichia coli bacteria. This discovery started a new chapter in medicinal chemistry and the interesting properties of cisplatin were soon applied in cancer therapy especially in curing genitourinary tumors. However, various side effects limited its use in medical treatment. Since then a great number of other metal-organic complexes based on platinum, palladium, ruthenium, gold, copper, silver, rhodium, osmium, rhenium, iridium and others have been synthesized. Among them, NAMI-A and KP1019 have recently undergone clinical trials. In this review paper we report a detailed account of metal complexes with phosphorus-based ligands which are of particular interest in therapeutics.

  14. Electrically driven rapidly vaporizing foils, wires and strips used for collision welding and sheet metal forming

    DOEpatents

    Vivek, Anupam; Daehn, Glenn S; Taber, Geoffrey A; Johnson, Jason R

    2015-05-05

    A method for forming a piece of a sheet metal is performed by positioning a consumable body, made of metal, proximate to the piece of the sheet metal. The consumable body is rapidly vaporized, and the gas pressure generated thereby is directed into the piece of the sheet metal. This results in acceleration of the piece of sheet metal, and it is collided into a stationary body at a velocity, generally in excess of 200 m/s. Depending upon the type of stationary body, the piece of sheet metal is deformed into a predetermined shape or is welded onto the stationary body. The vaporization is accomplished by passing a high current of electricity into the consumable body. The effect of the vaporized metal may be augmented by additional components in the consumable body.

  15. Process Simulation of Aluminium Sheet Metal Deep Drawing at Elevated Temperatures

    SciTech Connect

    Winklhofer, Johannes; Trattnig, Gernot; Sommitsch, Christof

    2010-06-15

    Lightweight design is essential for an economic and environmentally friendly vehicle. Aluminium sheet metal is well known for its ability to improve the strength to weight ratio of lightweight structures. One disadvantage of aluminium is that it is less formable than steel. Therefore complex part geometries can only be realized by expensive multi-step production processes. One method for overcoming this disadvantage is deep drawing at elevated temperatures. In this way the formability of aluminium sheet metal can be improved significantly, and the number of necessary production steps can thereby be reduced. This paper introduces deep drawing of aluminium sheet metal at elevated temperatures, a corresponding simulation method, a characteristic process and its optimization. The temperature and strain rate dependent material properties of a 5xxx series alloy and their modelling are discussed. A three dimensional thermomechanically coupled finite element deep drawing simulation model and its validation are presented. Based on the validated simulation model an optimised process strategy regarding formability, time and cost is introduced.

  16. Complex Dynamic Flows in Solar Flare Sheet Structures

    NASA Technical Reports Server (NTRS)

    McKenzie, David E.; Reeves, Katharine K.; Savage, Sabrina

    2012-01-01

    Observations of high-energy emission from solar flares often reveal the presence of large sheet-like structures, sometimes extending over a space comparable to the Sun's radius. Given that these structures are found between a departing coronal mass ejection and the post-eruption flare arcade, it is natural to associate the structure with a current sheet; though the relationship is unclear. Moreover, recent high-resolution observations have begun to reveal that the motions in this region are highly complex, including reconnection outflows, oscillations, and apparent wakes and eddies. We present a detailed first look at the complicated dynamics within this supra-arcade plasma, and consider implications for the interrelationship between the plasma and its embedded magnetic field.

  17. TSCA Chemical Data Reporting Fact Sheet: Reporting Manufactured Chemical Substances from Metal Mining and Related Activities

    EPA Pesticide Factsheets

    This fact sheet provides guidance on the Chemical Data Reporting (CDR) rule requirements related to the reporting of mined metals, intermediates, and byproducts manufactured during metal mining and related activities.

  18. Laser-Assisted Sheet Metal Working by the Integration of Scanner System Technology into a Progressive Die

    NASA Astrophysics Data System (ADS)

    Brecher, Christian; Emonts, Michael; Eckert, Markus

    Within the sheet metal working industry the demand for thinner sheet materials with very high strength is growing due to the increasing importance for saving energy and responsible usage of natural resources. High strength and low ductility restrict application of state-of-the-art technology to shear, bend or deep draw parts with the needed complexity and quality. The Fraunhofer IPT has developed a "hy-PRESS" system to combine laser-assisted preheating and conventional punching to a hybrid technology in a progressive die, which allows to shear, bend and deep draw high strength materials with a high quality and complexity in progressive dies.

  19. On The Prediction Of Plastic Instability In Metal Sheets

    SciTech Connect

    Mattiasson, Kjell; Sigvant, Mats; Larsson, Mats

    2007-05-17

    The current report presents some results from a study on the prediction of necking failure in ductile metal sheets. In particular methods for creating Forming Limit Curves (FLCs) are discussed in the present report. Three groups of methods are treated: Experimental methods, Theoretical/analytical methods, and the Finite Element Method (FEM). The various methods are applied to two different materials: An aluminum alloy and a high strength steel. These materials do both exhibit a distinct necking behavior before fracture, and they do both exhibit only a small strain rate dependence. As can be expected, the resulting FLCs from the various experimental, theoretical, and numerical methods show a substantial scatter. The reasons for these deviating results are analyzed, and some conclusions are drawn regarding the applicability of the different methods.

  20. Remapping algorithms: application to trimming operations in sheet metal forming

    NASA Astrophysics Data System (ADS)

    Neto, D. M.; Diogo, C. M. A.; Neves, T. F.; Oliveira, M. C.; Alves, J. L.; Menezes, L. F.

    2016-08-01

    Most of sheet metal forming processes comprise intermediate trimming operations to remove superfluous material. These operations are required for subsequent forming operations. On the other hand, the springback is strongly influenced by the trimming operations that change the part stiffness and the stress field. From the numerical point of view, this involves the geometrical trimming of the finite element mesh and subsequent remapping of the state variables. This study presents a remapping method based on Dual Kriging interpolation, specifically developed for hexahedral finite elements, which has been implemented in DD3TRIM in-house code. Its performance is compared with the one of the Incremental Volumetric Remapping method, using the split-ring test to highlight their advantages and limitations. The numerical simulation of the forming processes is performed with DD3IMP finite element solver.

  1. Process Windows for Sheet Metal Parts based on Metamodels

    NASA Astrophysics Data System (ADS)

    Harsch, D.; Heingärtner, J.; Hortig, D.; Hora, P.

    2016-08-01

    Achieving robust production of deep drawn sheet metal parts is challenging. The fluctuations of process and material properties often lead to robustness problems. Numerical simulations are used to validate the feasibility and to detect critical regions of a part. To enhance the consistency with the real process conditions, the measured material data and the force distribution are taken into account. The simulation metamodel contains the virtual knowledge of a particular forming process, which is determined based on a series of finite element simulations with variable input parameters. Based on the metamodels, process windows can be evaluated for different parameter configurations. This helps improving the operating point search, to adjust process settings if the process becomes unstable and to visualize the influence of arbitrary parameters on the process window.

  2. Quadratic solid-shell elements for nonlinear structural analysis and sheet metal forming simulation

    NASA Astrophysics Data System (ADS)

    Wang, Peng; Chalal, Hocine; Abed-Meraim, Farid

    2017-01-01

    In this paper, two quadratic solid-shell (SHB) elements are proposed for the three-dimensional modeling of thin structures. These consist of a 20-node hexahedral solid-shell element, denoted SHB20, and its 15-node prismatic counterpart, denoted SHB15. The formulation of these elements is extended in this work to include geometric and material nonlinearities, for application to problems involving large displacements and rotations as well as plasticity. For this purpose, the SHB elements are coupled with large-strain anisotropic elasto-plastic constitutive equations for metallic materials. Although based on a purely three-dimensional approach, several modifications are introduced in the formulation of these elements to provide them with interesting shell features. In particular, a special direction is chosen to represent the thickness, along which a user-defined number of integration points are located. Furthermore, for efficiency requirements and for alleviating locking phenomena, an in-plane reduced-integration scheme is adopted. The resulting formulations are implemented into the finite element software ABAQUS/Standard and, to assess their performance, a variety of nonlinear benchmark problems are investigated. Attention is then focused on the simulation of various complex sheet metal forming processes, involving large strain, anisotropic plasticity, and double-sided contact. From all simulation results, it appears that the SHB elements represent an interesting alternative to traditional shell and solid elements, due to their versatility and capability of accurately modeling selective nonlinear benchmark problems as well as complex sheet metal forming processes.

  3. Formazans and their metal complexes

    NASA Astrophysics Data System (ADS)

    Sigeikin, Gennadii I.; Lipunova, Galina N.; Pervova, I. G.

    2006-10-01

    The current data on the structure of formazans in crystals and in solutions are considered and some problems of tautomeric and conformational equilibria are discussed. Some novel classes of formazans synthesised over the past decade are presented. The results of structural studies of formazan complexes with various types of metal coordination are generalised. Examples of synthesis of formazan-containing polymers are given. Special emphasis is placed on analytical and practical applications of formazan derivatives.

  4. Determination of Anisotropic Hardening of Sheet Metals by Shear Tests

    SciTech Connect

    Schikorra, Marco; Brosius, Alexander; Kleiner, Matthias

    2005-08-05

    With regard to the increasing necessity of accurate material data determination for the prediction of springback, a material testing equipment has been developed and set up for the measurement of material hardening within cyclic loading. One reason for inaccurate springback predictions can be seen in a missing consideration of load reversal effects in a realistic material model description. Due to bending and unbending while the material is drawn from the flange over a radius of a deep drawing tool, a hardening takes place which leads to an expanding or shifting of the elastic area and yield locus known as isotropic, kinematic, or combined hardening. Since springback is mainly influenced by the actual stress state and a correct distinction between elastic and elastic-plastic regions, an accurate prediction of these stress and strain components is basically required to simulate springback accurately, too. The presented testing method deals with shearing of sheet metal specimens in one or more load cycles to analyze the change of yield point and yield curve. The experimental set up is presented and discussed and the results are shown for different materials such as aluminum A199.5, stainless steel X5CrNi18.10, dual phase steel DP600, and copper Cu99.99. To guarantee a wide experimental range, different sheet thicknesses were used additionally. Simulations using the finite element method were carried out to compare the measured results with calculated results from different yield criterions and different hardening laws mentioned above. It was possible to show that commonly used standard material hardening laws like isotropic and kinematic hardening laws often do not lead to accurate stress state predictions when load reversals occur. The work shows the range of occurring differences and strategies to obtain to a more reliable prediction.

  5. Simulation of stress in an innovative combination of composite with metal sheet

    NASA Astrophysics Data System (ADS)

    Wróbel, A.; Płaczek, M.; Buchacz, A.; Słomiany, A.

    2016-08-01

    In this article research of stress impact in multi-point connection glass epoxy composite with a metal sheet with a rivet nuts was presented. Composite materials are increasingly used because of the good mechanical properties and low price. The laminates are composites of a layer structure, characterized by very high strength in the direction of the fibers, their weakness is not good toughness in a direction perpendicular to the layers. Mainly checking of displacements and stresses generated on the sheet as a result of pneumatic actuators load for composite boards was carried out. Glass-epoxy composite consisting of four layers of glass mat with a weight of 1000 g/m2 and an epoxy resin and hardener HG700 LG700 volume ratio of 38/100 was created. Next composite was fixed with steel plate with a rivet nuts and bolts. A model of laminate samples and plate was simulate in Siemens NX 8.5 software. The simulation results will determine stresses and displacements in conjunction newly designed composite sheet. Strength analysis was performed with the use of the module NX Advanced Simulation. FEM is an advanced method for solving systems of differential equations, based on the division of the field into finite elements for which the solution is approximated by specific functions, and performing the actual calculations only for nodes of this division. Due to the complexity of the created object to simplify the elements made to reduce the calculation time. This article presents the study of stresses and displacements in the composite plates joined with sheet metal, in summary of this article, the authors compare the obtainted results with the computer simulation results in the article: " The study of fix composite panel and steel plates on testing stand".

  6. Complex Dynamic Flows in Solar Flare Sheet Structures

    NASA Astrophysics Data System (ADS)

    McKenzie, David Eugene; Reeves, K. K.; Savage, S. L.

    2012-05-01

    Observations of high-energy emission from solar flares often reveal the presence of large sheet-like structures, sometimes extending over a space comparable to the Sun's radius. Given that these structures are found between a departing coronal mass ejection and the post-eruption flare arcade, it is natural to associate the structure with a current sheet; though the relationship is unclear. Moreover, recent high-resolution observations have begun to reveal that the motions in this region are highly complex, including reconnection outflows, oscillations, and apparent wakes and eddies. We present a detailed first look at the complicated dynamics within this supra-arcade plasma, and consider implications for the interrelationship between the plasma and its embedded magnetic field. This work is supported by NASA under contract SP02H3901R from Lockheed-Martin to MSU (DMcK), contract SP02H1701R from Lockheed-Martin to SAO (KKR), and contract NNM07AB07C with the Harvard-Smithsonian Astrophysical Observatory. SLS is supported via a NASA/GSFC NPP appointment administered by Oak Ridge Associated Universities and under the mentorship of G. Holman.

  7. An ice sheet model of reduced complexity for paleoclimate studies

    NASA Astrophysics Data System (ADS)

    Neff, Basil; Born, Andreas; Stocker, Thomas F.

    2016-04-01

    IceBern2D is a vertically integrated ice sheet model to investigate the ice distribution on long timescales under different climatic conditions. It is forced by simulated fields of surface temperature and precipitation of the Last Glacial Maximum and present-day climate from a comprehensive climate model. This constant forcing is adjusted to changes in ice elevation. Due to its reduced complexity and computational efficiency, the model is well suited for extensive sensitivity studies and ensemble simulations on extensive temporal and spatial scales. It shows good quantitative agreement with standardized benchmarks on an artificial domain (EISMINT). Present-day and Last Glacial Maximum ice distributions in the Northern Hemisphere are also simulated with good agreement. Glacial ice volume in Eurasia is underestimated due to the lack of ice shelves in our model. The efficiency of the model is utilized by running an ensemble of 400 simulations with perturbed model parameters and two different estimates of the climate at the Last Glacial Maximum. The sensitivity to the imposed climate boundary conditions and the positive degree-day factor β, i.e., the surface mass balance, outweighs the influence of parameters that disturb the flow of ice. This justifies the use of simplified dynamics as a means to achieve computational efficiency for simulations that cover several glacial cycles. Hysteresis simulations over 5 million years illustrate the stability of the simulated ice sheets to variations in surface air temperature.

  8. New Approaches on Automated Wrinkle Detection in Sheet Metal Components by Forming Simulation

    NASA Astrophysics Data System (ADS)

    Liewald, M.; Wurster, K.; Blaich, C.

    2011-05-01

    In production of passenger cars, geometry complexity of deep drawn body panels increases constantly. For that reason, sheet metal components are analyzed within finite element analysis (FEA) with regard to their feasibility in production and expected quality before production equipment, such as drawing dies, is manufactured. Main criteria for characterizing component quality are cracks and sidewall wrinkles. In particular, cracks occur due to local overload in sheet metal plane caused by inadequate process parameters such as too high friction or forming forces. In contrast, sidewall wrinkles are caused by an inadequate level of compressive stress in component areas without contact between sheet metal component and drawing die. In FEA, failure by cracks can be analyzed evaluating scalar values of thinning or strain distribution in forming limit diagram with regard to forming limit curve. In contrast, detecting sidewall wrinkles often requires a manual and visual inspection of simulation results by the user. Therefore, a procedure to detect sidewall wrinkles in an automated manner is presented in this paper. The presented method determines occurrence of sidewall wrinkles based on strain distribution in forming limit diagram. Utilization of the disclosed calculation strategy allows estimation of cracks and sidewall wrinkles simultaneously after one run of simulation code. The presented approach for automated detection of sidewall wrinkles in combination with multivariate statistics shows a tool for virtual engineering to optimize deep drawing processes. Prior to die manufacturing, optimization with regard to both sides of the process window is possible. Hence, an increase in design efficiency, design space and reduction of development time and costs can be achieved at the same time.

  9. Towards Industrial Application of Damage Models for Sheet Metal Forming

    NASA Astrophysics Data System (ADS)

    Doig, M.; Roll, K.

    2011-05-01

    Due to global warming and financial situation the demand to reduce the CO2-emission and the production costs leads to the permanent development of new materials. In the automotive industry the occupant safety is an additional condition. Bringing these arguments together the preferable approach for lightweight design of car components, especially for body-in-white, is the use of modern steels. Such steel grades, also called advanced high strength steels (AHSS), exhibit a high strength as well as a high formability. Not only their material behavior but also the damage behavior of AHSS is different compared to the performances of standard steels. Conventional methods for the damage prediction in the industry like the forming limit curve (FLC) are not reliable for AHSS. Physically based damage models are often used in crash and bulk forming simulations. The still open question is the industrial application of these models for sheet metal forming. This paper evaluates the Gurson-Tvergaard-Needleman (GTN) model and the model of Lemaitre within commercial codes with a goal of industrial application.

  10. Exploring the Cellular Accumulation of Metal Complexes

    PubMed Central

    Puckett, Cindy A.; Ernst, Russell J.; Barton, Jacqueline K.

    2010-01-01

    Transition metal complexes offer great potential as diagnostic and therapeutic agents, and a growing number of biological applications have been explored. To be effective, these complexes must reach their intended target inside the cell. Here we review the cellular accumulation of metal complexes, including their uptake, localization, and efflux. Metal complexes are taken up inside cells through various mechanisms, including passive diffusion and entry through organic and metal transporters. Emphasis is placed on the methods used to examine cellular accumulation, to identify the mechanism(s) of uptake, and to monitor possible efflux. Conjugation strategies that have been employed to improve the cellular uptake characteristics of metal complexes are also described. PMID:20104335

  11. Theoretical study of binding of metal-doped graphene sheet and carbon nanotubes with dioxin.

    PubMed

    Kang, Hong Seok

    2005-07-13

    Using density functional theory, we have theoretically studied dioxin binding on a graphene sheet or carbon nanotubes (CNT), finding that they can be effective adsorbents for dioxin in the presence of calcium atoms. This is due to a cooperative formation of sandwich complexes of graphene sheet or (5,5) CNT through the interaction pi-Ca-pi with the total binding energy of more than 3 eV. This correlates with the band structure analysis, which indicates charge transfer from the carbon systems and calcium atoms to dioxin when the molecule binds to the metal-doped carbon systems. For CNT with small radii, the relative strength of CNT-dioxin interaction is dependent on their chiralities. Upon dioxin binding, a large increase in the electronic density of states near the Fermi level also suggests that they can be used for dioxin sensing. Fe-doped CNT is also found to bind dioxin strongly, revealing an important role played by remnants of metallic catalysts in the chemical properties of CNT.

  12. Steel--Project Fact Sheet: Recycling Acid and Metal Salts from Pickling Liquors

    SciTech Connect

    Poole, L.; Recca, L.

    1999-01-14

    Regenerating hydrochloric acids from metal finishing pickling baths reduces costs, wastes, and produces a valuable by-product--ferrous sulfate. Order your copy of this OIT project fact sheet and learn more about how your company can benefit.

  13. Numerical assessment of residual formability in sheet metal products: towards design for sustainability

    NASA Astrophysics Data System (ADS)

    Falsafi, Javad; Demirci, Emrah; Silberschmidt, Vadim. V.

    2016-08-01

    A new computational scheme is presented to addresses cold recyclability of sheet- metal products. Cold recycling or re-manufacturing is an emerging area studied mostly empirically; in its current form, it lacks theoretical foundation especially in the area of sheet metals. In this study, a re-formability index was introduced based on post-manufacture residual formability in sheet metal products. This index accounts for possible levels of deformation along different strain paths based on Polar Effective Plastic Strain (PEPS) technique. PEPS is strain-path independent, hence provides a foundation for residual formability analysis. A user- friendly code was developed to implement this assessment in conjunction with advanced finite- element (FE) analysis. The significance of this approach is the advancement towards recycling of sheet metal products without melting them.

  14. Numerical simulation of energy-absorbing capacity of metal sheet under penetration

    NASA Astrophysics Data System (ADS)

    Kaminishi, K.

    1997-07-01

    A finite element program employing a new explicit and consistent scheme for dynamic plasticity problems has been developed and deformation analysis of metal sheet under penetration has been carried out by this program. On the basis of this simulation, formulae for estimating the energy-absorbing capacity of thin metal sheet are proposed and the validity of this formulae has been shown numerically and experimentally.

  15. A new strategy for stiffness evaluation of sheet metal parts

    NASA Astrophysics Data System (ADS)

    Cai, Q.; Volk, W.; Düster, A.; Rank, E.

    2011-08-01

    In the automotive industry, surfaces of styling models are shaped very often in physical models. For example, in the styling process of a car body important design work is realized by clay models and the resulting geometry information typically comes from optical scans. The scanned data is given in the form of point clouds which is then utilized in the virtual planning process for engineering work, e.g. to evaluate the load-carrying capacity. This is an important measure for the stiffness of the car body panels. In this contribution, the following two issues are discussed: what is the suitable geometric representation of the stiffness of the car body and how it is computed if only discrete point clouds exist. In the first part, the suitable geometric representation is identified by constructing continuous CAD models with different geometric parameters, e.g. Gaussian curvature and mean curvature. The stiffness of models is then computed in LS-DYNA and the influence of different geometric parameters is presented based on the simulation result. In the second part, the point clouds from scanned data, rather than continuous CAD models, are directly utilized to estimate the Gaussian curvature, which is normally derived from continuous surfaces. The discrete Gauss-Bonnet algorithm is applied to estimate the Gaussian curvature of the point clouds and the sensitivity of the algorithm with respect to the mesh quality is analyzed. In this way, the stiffness evaluation process in an early stage can be accelerated since the transformation from discrete data to continuous CAD data is labor-intensive. The discrete Gauss-Bonnet algorithm is finally applied to a sheet metal model of the BMW 3 series.

  16. Electro-Hydraulic Forming of Sheet Metals: Free-forming vs. Conical-die Forming

    SciTech Connect

    Rohatgi, Aashish; Stephens, Elizabeth V.; Davies, Richard W.; Smith, Mark T.; Soulami, Ayoub; Ahzi, Said

    2012-05-01

    This work builds upon our recent advances in quantifying high-rate deformation behavior of sheet metals, during electro-hydraulic forming (EHF), using high-speed imaging and digital image correlation techniques. Following recent publication of an earlier manuscript, resulting from this project, in the Journal of Materials Processing Technology, this manuscript further details our results and compares forming behavior when the process is carried out inside an open-die or a conical die. It is anticipated that quantitative information of the sheet deformation history, made possible by the experimental technique developed in this work, will improve our understanding on the roles of strain-rate and sheet-die interactions in enhancing the sheet metal formability during high-rate forming. This knowledge will be beneficial to the automotive industry and enable them to fabricate light-weight sheet parts out of Al and advanced high strength steels.

  17. Laser altimetry reveals complex pattern of Greenland Ice Sheet dynamics.

    PubMed

    Csatho, Beata M; Schenk, Anton F; van der Veen, Cornelis J; Babonis, Gregory; Duncan, Kyle; Rezvanbehbahani, Soroush; van den Broeke, Michiel R; Simonsen, Sebastian B; Nagarajan, Sudhagar; van Angelen, Jan H

    2014-12-30

    We present a new record of ice thickness change, reconstructed at nearly 100,000 sites on the Greenland Ice Sheet (GrIS) from laser altimetry measurements spanning the period 1993-2012, partitioned into changes due to surface mass balance (SMB) and ice dynamics. We estimate a mean annual GrIS mass loss of 243 ± 18 Gt ⋅ y(-1), equivalent to 0.68 mm ⋅ y(-1) sea level rise (SLR) for 2003-2009. Dynamic thinning contributed 48%, with the largest rates occurring in 2004-2006, followed by a gradual decrease balanced by accelerating SMB loss. The spatial pattern of dynamic mass loss changed over this time as dynamic thinning rapidly decreased in southeast Greenland but slowly increased in the southwest, north, and northeast regions. Most outlet glaciers have been thinning during the last two decades, interrupted by episodes of decreasing thinning or even thickening. Dynamics of the major outlet glaciers dominated the mass loss from larger drainage basins, and simultaneous changes over distances up to 500 km are detected, indicating climate control. However, the intricate spatiotemporal pattern of dynamic thickness change suggests that, regardless of the forcing responsible for initial glacier acceleration and thinning, the response of individual glaciers is modulated by local conditions. Recent projections of dynamic contributions from the entire GrIS to SLR have been based on the extrapolation of four major outlet glaciers. Considering the observed complexity, we question how well these four glaciers represent all of Greenland's outlet glaciers.

  18. Magma transport in sheet intrusions of the Alnö carbonatite complex, central Sweden

    PubMed Central

    Andersson, Magnus; Almqvist, Bjarne S. G.; Burchardt, Steffi; Troll, Valentin R.; Malehmir, Alireza; Snowball, Ian; Kübler, Lutz

    2016-01-01

    Magma transport through the Earth’s crust occurs dominantly via sheet intrusions, such as dykes and cone-sheets, and is fundamental to crustal evolution, volcanic eruptions and geochemical element cycling. However, reliable methods to reconstruct flow direction in solidified sheet intrusions have proved elusive. Anisotropy of magnetic susceptibility (AMS) in magmatic sheets is often interpreted as primary magma flow, but magnetic fabrics can be modified by post-emplacement processes, making interpretation of AMS data ambiguous. Here we present AMS data from cone-sheets in the Alnö carbonatite complex, central Sweden. We discuss six scenarios of syn- and post-emplacement processes that can modify AMS fabrics and offer a conceptual framework for systematic interpretation of magma movements in sheet intrusions. The AMS fabrics in the Alnö cone-sheets are dominantly oblate with magnetic foliations parallel to sheet orientations. These fabrics may result from primary lateral flow or from sheet closure at the terminal stage of magma transport. As the cone-sheets are discontinuous along their strike direction, sheet closure is the most probable process to explain the observed AMS fabrics. We argue that these fabrics may be common to cone-sheets and an integrated geology, petrology and AMS approach can be used to distinguish them from primary flow fabrics. PMID:27282420

  19. Magma transport in sheet intrusions of the Alnö carbonatite complex, central Sweden.

    PubMed

    Andersson, Magnus; Almqvist, Bjarne S G; Burchardt, Steffi; Troll, Valentin R; Malehmir, Alireza; Snowball, Ian; Kübler, Lutz

    2016-06-10

    Magma transport through the Earth's crust occurs dominantly via sheet intrusions, such as dykes and cone-sheets, and is fundamental to crustal evolution, volcanic eruptions and geochemical element cycling. However, reliable methods to reconstruct flow direction in solidified sheet intrusions have proved elusive. Anisotropy of magnetic susceptibility (AMS) in magmatic sheets is often interpreted as primary magma flow, but magnetic fabrics can be modified by post-emplacement processes, making interpretation of AMS data ambiguous. Here we present AMS data from cone-sheets in the Alnö carbonatite complex, central Sweden. We discuss six scenarios of syn- and post-emplacement processes that can modify AMS fabrics and offer a conceptual framework for systematic interpretation of magma movements in sheet intrusions. The AMS fabrics in the Alnö cone-sheets are dominantly oblate with magnetic foliations parallel to sheet orientations. These fabrics may result from primary lateral flow or from sheet closure at the terminal stage of magma transport. As the cone-sheets are discontinuous along their strike direction, sheet closure is the most probable process to explain the observed AMS fabrics. We argue that these fabrics may be common to cone-sheets and an integrated geology, petrology and AMS approach can be used to distinguish them from primary flow fabrics.

  20. Photochemistry of Metal-Metal Bonded Transition Element Complexes

    DTIC Science & Technology

    1980-12-12

    CONTRACT NO0014-75-C-0880 Task No. NR 051-579 TECHNICAL REPORT NO. 25 PHOTOCHEMISTRY OF METAL-METAL BONDED TRANSITION ELEMENT COMPLEXES by Mark S . Wrighton...unlimited. 17, Di:- t. Ii t I / Avolil:J, ; Codc’s ! Photochemistry of Metal-Metal Bonded Transition Element Complexes Mark S . Wrighton, James L. Graff...publication in the ACS Symposium Series, "Reactivity of MetalrMetal Bonds", M. H. Chisholm, ed.) IA c*Addre~ s orrespondence to this author, ; r[ I . - - 1

  1. Aircraft Assembly, Riveting and Surface Repair 1; Sheet Metal Work 2: 9855.02.

    ERIC Educational Resources Information Center

    Dade County Public Schools, Miami, FL.

    The course outline will serve as a guide to the 11th grade student interested in sheet metal occupations. The course, 135 hours in length, covers the basic techniques of cutting and trimming, drilling and hole preparation of metals. Lecture and demonstration techniques are to be utilized, with emphasis on the use of visual aids, mock-ups,…

  2. Residual Stress In Sheet Metal Parts Made By Incremental Forming Process

    SciTech Connect

    Tanaka, Shigekazu; Nakamura, Tamotsu; Hayakawa, Kunio; Nakamura, Hideo; Motomura, Kazuo

    2007-05-17

    Incremental sheet metal forming, which uses a CNC forming stylus, is new flexible forming process not requiring the use of any expensive dies. We have applied the incremental forming process to dental prosthesis. This new process, however, posed difficult problems. After removing the outer portion of the incremental formed sheet metal part, the inner part is distorted. In this paper, the residual stress in the sheet metal part obtained by incremental forward stretch forming operations has been examined. Numerical simulations were conducted for solid elements. When small rigid ball slides on the metal sheet with a certain vertical feed, tension residual stress is produced in the upper layer of the sheet and compression stress in the lower. Then, the resultant moments throughout the sheet cause negative spring-back when the outer portion is removed. A systematic study of the behavior was conducted in this paper. Parameters considered included the tool radius and the vertical tool feed rate. The tip radius of forming stylus has a significant influence on the residual stress. The smaller radius of forming stylus, the larger bending force becomes. And new process with double forming styluses is examined to reduce the bending force.

  3. Laser altimetry reveals complex pattern of Greenland Ice Sheet dynamics

    PubMed Central

    Csatho, Beata M.; Schenk, Anton F.; van der Veen, Cornelis J.; Babonis, Gregory; Duncan, Kyle; Rezvanbehbahani, Soroush; van den Broeke, Michiel R.; Simonsen, Sebastian B.; Nagarajan, Sudhagar; van Angelen, Jan H.

    2014-01-01

    We present a new record of ice thickness change, reconstructed at nearly 100,000 sites on the Greenland Ice Sheet (GrIS) from laser altimetry measurements spanning the period 1993–2012, partitioned into changes due to surface mass balance (SMB) and ice dynamics. We estimate a mean annual GrIS mass loss of 243 ± 18 Gt⋅y−1, equivalent to 0.68 mm⋅y−1 sea level rise (SLR) for 2003–2009. Dynamic thinning contributed 48%, with the largest rates occurring in 2004–2006, followed by a gradual decrease balanced by accelerating SMB loss. The spatial pattern of dynamic mass loss changed over this time as dynamic thinning rapidly decreased in southeast Greenland but slowly increased in the southwest, north, and northeast regions. Most outlet glaciers have been thinning during the last two decades, interrupted by episodes of decreasing thinning or even thickening. Dynamics of the major outlet glaciers dominated the mass loss from larger drainage basins, and simultaneous changes over distances up to 500 km are detected, indicating climate control. However, the intricate spatiotemporal pattern of dynamic thickness change suggests that, regardless of the forcing responsible for initial glacier acceleration and thinning, the response of individual glaciers is modulated by local conditions. Recent projections of dynamic contributions from the entire GrIS to SLR have been based on the extrapolation of four major outlet glaciers. Considering the observed complexity, we question how well these four glaciers represent all of Greenland’s outlet glaciers. PMID:25512537

  4. Study of Microstructure and Mechanical Properties Effects on Workpiece Quality in Sheet Metal Extrusion Process.

    PubMed

    Suriyapha, Chatkaew; Bubphachot, Bopit; Rittidech, Sampan

    2015-01-01

    Sheet metal extrusion is a metal forming process in which the movement of a punch penetrates a sheet metal surface and it flows through a die orifice; the extruded parts can be deflected to have an extrusion cavity and protrusion on the opposite side. Therefore, this process results in a narrow region of highly localized plastic deformation due to the formation and microstructure effect on the work piece. This research investigated the characteristics of the material-flow behavior during the formation and its effect on the microstructure of the extruded sheet metal using the finite element method (FEM). The actual parts and FEM simulation model were developed using a blank material made from AISI-1045 steel with a thickness of 5 mm; the material's behavior was determined subject to the punch penetration depths of 20%, 40%, 60%, and 80% of the sheet thickness. The results indicated the formation and microstructure effects on the sheet metal extrusion parts and defects. Namely, when increasing penetration, narrowing the die orifice the material flows through, the material was formed by extruding, and defects were visibility, and the microstructure of the material's grains' size was flat and very fine. Extrusion defects were not found in the control material flow. The region of highly localized plastic deformation affected the material gain and mechanical properties. The FEM simulation results agreed with the experimental results. Moreover, FEM could be investigated as a tool to decrease the cost and time in trial and error procedures.

  5. Resistance Spot Welding of AA5052 Sheet Metal of Dissimilar Thickness

    NASA Astrophysics Data System (ADS)

    Mat Din, N. A.; Zuhailawati, H.; Anasyida, A. S.

    2016-02-01

    Resistance spot welding of dissimilar thickness of AA5052 aluminum alloy was performed in order to investigate the effect of metal thickness on the weldment strength. Resistance spot welding was done using a spot welder machine available in Coraza Systems Sdn Bhd using a hemispherical of chromium copper electrode tip with radius of 6.00 mm under 14 kA of current and 0.02 bar of pressure for all thickness combinations. Lap joint configuration was produced between 2.0 mm thick sheet and 1.2 - 3.2 mm thick sheet, respectively. Microstructure of joint showed asymmetrical nugget shape that was larger on the thicker side indicating larger molten metal volume. Joint 2.0 mm x 3.2 mm sheets has the lowest hardness in both transverse direction and through thickness direction because less heat left in the weld nugget. The microstructure shows that this joint has coarse grains of HAZ. As thickness of sheet metal increased, the failure load of the joints increased. However, there was no linear correlation established between joint strength and metal thickness due to different shape of fusion zone in dissimilar thickness sheet metal.

  6. High Operating Temperature Liquid Metal Heat Transfer Fluids (Fact Sheet)

    SciTech Connect

    Not Available

    2012-12-01

    The University of California, Los Angeles, the University of California, Berkeley, and Yale University is one of the 2012 SunShot CSP R&D awardees for their Multidisciplinary University Research Initiative (MURI): High Operating Temperature (HOT) Fluids. This fact sheet explains the motivation, description, and impact of the project.

  7. Assessing the formability of metallic sheets by means of localized and diffuse necking models

    NASA Astrophysics Data System (ADS)

    Comşa, Dan-Sorin; Lǎzǎrescu, Lucian; Banabic, Dorel

    2016-10-01

    The main objective of the paper consists in elaborating a unified framework that allows the theoretical assessment of sheet metal formability. Hill's localized necking model and the Extended Maximum Force Criterion proposed by Mattiasson, Sigvant, and Larsson have been selected for this purpose. Both models are thoroughly described together with their solution procedures. A comparison of the theoretical predictions with experimental data referring to the formability of a DP600 steel sheet is also presented by the authors.

  8. Development of Multi-Scale Finite Element Analysis Codes for High Formability Sheet Metal Generation

    SciTech Connect

    Nnakamachi, Eiji; Kuramae, Hiroyuki; Ngoc Tam, Nguyen; Nakamura, Yasunori; Sakamoto, Hidetoshi; Morimoto, Hideo

    2007-05-17

    In this study, the dynamic- and static-explicit multi-scale finite element (F.E.) codes are developed by employing the homogenization method, the crystalplasticity constitutive equation and SEM-EBSD measurement based polycrystal model. These can predict the crystal morphological change and the hardening evolution at the micro level, and the macroscopic plastic anisotropy evolution. These codes are applied to analyze the asymmetrical rolling process, which is introduced to control the crystal texture of the sheet metal for generating a high formability sheet metal. These codes can predict the yield surface and the sheet formability by analyzing the strain path dependent yield, the simple sheet forming process, such as the limit dome height test and the cylindrical deep drawing problems. It shows that the shear dominant rolling process, such as the asymmetric rolling, generates ''high formability'' textures and eventually the high formability sheet. The texture evolution and the high formability of the newly generated sheet metal experimentally were confirmed by the SEM-EBSD measurement and LDH test. It is concluded that these explicit type crystallographic homogenized multi-scale F.E. code could be a comprehensive tool to predict the plastic induced texture evolution, anisotropy and formability by the rolling process and the limit dome height test analyses.

  9. Computer aided process planning and die design in simulation environment in sheet metal forming

    NASA Astrophysics Data System (ADS)

    Tisza, Miklós; Lukács, Zsolt

    2013-12-01

    During the recent 10-15 years, Computer Aided Process Planning and Die Design evolved as one of the most important engineering tools in sheet metal forming, particularly in the automotive industry. This emerging role is strongly emphasized by the rapid development of Finite Element Modeling, as well. The purpose of this paper is to give a general overview about the recent achievements in this very important field of sheet metal forming and to introduce some special results in this development activity. Therefore, in this paper, an integrated process simulation and die design system developed at the University of Miskolc, Department of Mechanical Engineering will be analyzed. The proposed integrated solutions have great practical importance to improve the global competitiveness of sheet metal forming in the very important segment of industry. The concept described in this paper may have specific value both for process planning and die design engineers.

  10. Influence of part orientation on the geometric accuracy in robot-based incremental sheet metal forming

    NASA Astrophysics Data System (ADS)

    Störkle, Denis Daniel; Seim, Patrick; Thyssen, Lars; Kuhlenkötter, Bernd

    2016-10-01

    This article describes new developments in an incremental, robot-based sheet metal forming process (`Roboforming') for the production of sheet metal components for small lot sizes and prototypes. The dieless kinematic-based generation of the shape is implemented by means of two industrial robots, which are interconnected to a cooperating robot system. Compared to other incremental sheet metal forming (ISF) machines, this system offers high geometrical form flexibility without the need of any part-dependent tools. The industrial application of ISF is still limited by certain constraints, e.g. the low geometrical accuracy. Responding to these constraints, the authors present the influence of the part orientation and the forming sequence on the geometric accuracy. Their influence is illustrated with the help of various experimental results shown and interpreted within this article.

  11. Advances in post-necking flow curve identification of sheet metal through standard tensile testing

    NASA Astrophysics Data System (ADS)

    Coppieters, Sam; Cooreman, Steven; Debruyne, Dimitri; Kuwabara, Toshihiko

    2013-12-01

    The standard tensile test is still the most common material test to identify the hardening behavior of sheet metal. When using standard equipment and well-known analytical formulas, however, the hardening behavior can only be identified up to the point of maximum uniform elongation. Several methods which deal with the problem of extended flow curve identification of sheet metal through a tensile test have been proposed in the past. This paper gives an overview of the four classes of methods to identify post-necking hardening behavior of sheet metal through tensile testing. In addition, identification methods from the first (average values across the neck), second (Bridgeman correction, modified Siebel and Schwaigerer correction) and third class (special case of the VFM) are used to identify the post-necking hardening behavior of DC05. Finally, these results are used to assess the validity of the different methods.

  12. A generalized quadratic flow law for sheet metals

    NASA Astrophysics Data System (ADS)

    Jones, S. E.; Gillis, P. P.

    1984-01-01

    A planar quadratic flow law is proposed for anisotropic sheet materials. This law is similar to the anisotropic strength criterion of Tsai and Wu. It has six experimentally determinable coefficients as compared to four in Hill’s flow law and, thus, allows more experimental information to be accommodated. However, the resulting strain increment vector, while unique, is not necessarily normal to the flow surface.

  13. On the formability, geometrical accuracy, and surface quality of sheet metal parts produced by SPIF

    NASA Astrophysics Data System (ADS)

    Alves, M. L.; Silva, M. B.; Alves, L. M.; Martins, P. A. F.

    2008-11-01

    Conventional sheet metal forming processes are not suitable for flexible small-batch production and, therefore, are not appropriate for the growing agile manufacturing trends requiring very short life-cycles, development and production lead times. In fact, the present need for flexible sheet metal forming techniques requires the development of innovative technological solutions that are capable of reducing the fixed and capital costs of sheet metal forming to a level where small-batch production becomes economically feasible. Single point incremental forming (SPIF) is a new sheet metal forming process with a high potential economic payoff for rapid prototyping applications and for small quantity production. In general terms a typical SPIF set-up makes use of a small number of low cost active tools components; (i) a blankholder, (ii) a backing plate and (iii) a single point forming tool. The tool path is generated in a CNC machining center and during the process there is no backup die supporting the back surface of the sheet. Despite the contributions of many researchers on the development of industrial applications and better characterization of the forming limits of the process, several key topics related to the mechanics of deformation, likely mode of failure, geometric accuracy and surface quality of the formed parts remain little understood and scarcely systematized. This paper attempts to provide new contributions about the abovementioned issues by means of a comprehensive experimental investigation performed under laboratory controlled conditions.

  14. Change in prevalence of asbestos-related disease among sheet metal workers 1986 to 2004.

    PubMed

    Welch, Laura S; Haile, Elizabeth; Dement, John; Michaels, David

    2007-03-01

    In 1985, the Sheet Metal Workers International Association and the Sheet Metal and Air Conditioning National Association formed The Sheet Metal Occupational Health Institute Trust to examine the health hazards of the sheet metal industry in the United States and Canada. Between 1986 and 2004, 18,211 individuals were examined. The mean age of this cohort was 57.9 years, and the participants had worked for a mean (+/- SD) duration of 32.9 +/- 6 years in the sheet metal trade. Twenty-three percent of participants were current smokers, 49% were former smokers, and 28% were never-smokers. A total of 9.6% of participants (1,745 participants) had findings that were consistent with parenchymal disease (International Labor Organization [ILO] score, >/= 1/0); 60% of those with an ILO score >/= 1/0 were classified as 1/0, 34% as 1/1 to 1/2, and 6% as >/= 2/1. A total of 21% of participants (3,827 participants) had pleural scarring. There was a lower prevalence of nonmalignant asbestos-related disease among those who began to work after 1970, when compared to workers who began to work before 1949; those who began to work between 1950 and 1969 had a prevalence between the other two groups. The strongest predictor of both parenchymal and pleural disease on a chest radiograph was the calendar year in which the worker began sheet metal work; work in a shipyard was also an important risk. The results of this study suggest that the efforts to reduce asbestos exposure in the 1980s through strengthened Occupational Safety and Health Administration regulation have had a positive public health impact.

  15. Calculation of electromagnetic force in electromagnetic forming process of metal sheet

    SciTech Connect

    Xu Da; Liu Xuesong; Fang Kun; Fang Hongyuan

    2010-06-15

    Electromagnetic forming (EMF) is a forming process that relies on the inductive electromagnetic force to deform metallic workpiece at high speed. Calculation of the electromagnetic force is essential to understand the EMF process. However, accurate calculation requires complex numerical solution, in which the coupling between the electromagnetic process and the deformation of workpiece needs be considered. In this paper, an appropriate formula has been developed to calculate the electromagnetic force in metal work-piece in the sheet EMF process. The effects of the geometric size of coil, the material properties, and the parameters of discharge circuit on electromagnetic force are taken into consideration. Through the formula, the electromagnetic force at different time and in different positions of the workpiece can be predicted. The calculated electromagnetic force and magnetic field are in good agreement with the numerical and experimental results. The accurate prediction of the electromagnetic force provides an insight into the physical process of the EMF and a powerful tool to design optimum EMF systems.

  16. An insight into fluorescent transition metal complexes.

    PubMed

    Chia, Y Y; Tay, M G

    2014-09-21

    The emission from transition metal complexes is usually produced from triplet excited states. Owing to strong spin-orbit coupling (SOC), the fast conversion of singlet to triplet excited states via intersystem crossing (ISC) is facilitated. Hence, in transition metal complexes, emission from singlet excited states is not favoured. Nevertheless, a number of examples of transition metal complexes that fluoresce with high intensity have been found and some of them were even comprehensively studied. In general, three common photophysical characteristics are used for the identification of fluorescent emission from a transition metal complex: emission lifetimes on the nanosecond scale; a small Stokes shift; and intense emission under aerated conditions. For most of the complexes reviewed here, singlet emission is the result of ligand-based fluorescence, which is the dominant emission process due to poor metal-ligand interactions leading to a small metal contribution in the excited states, and a competitive fluorescence rate constant when compared to the ISC rate constant. In addition to the pure fluorescence from metal complexes, another two types of fluorescent emissions were also reviewed, namely, delayed fluorescence and fluorescence-phosphorescence dual emissions. Both emissions also have their respective unique characteristics, and thus they are discussed in this perspective.

  17. Magnetohydrodynamic stability in the electromagnetic levitation of horizontal molten-metal sheets

    NASA Astrophysics Data System (ADS)

    Hull, John R.; Wiencek, Tom; Rote, Donald M.

    1989-06-01

    High-frequency electromagnetic (EM) fields are investigated for the levitation of thin horizontal sheets of liquid metal. A magnetic configuration is analyzed in which inductance stabilization provides global stability and magnetic flux compression provides local stability. Stability analysis indicates that frequencies greater than about 24 kHz are desirable to stably levitate 6 mm thick steel. For stability in systems without active feedback, a conducting screen is required below the metal, with a gap between the screen and the molten metal of no more than twice the metal thickness. Experiments in which 10 kHz EM fields were used to statically levitate sheets of molten tin indicate that dominant magnetohydrodynamic instabilities are of the Rayleigh-Taylor type and correspond to theory.

  18. 48 CFR 53.301-1427 - Standard Form 1427, Inventory Schedule A-Construction Sheet (Metals in Mill Product Form).

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 48 Federal Acquisition Regulations System 2 2010-10-01 2010-10-01 false Standard Form 1427, Inventory Schedule A-Construction Sheet (Metals in Mill Product Form). 53.301-1427 Section 53.301-1427... Illustrations of Forms 53.301-1427 Standard Form 1427, Inventory Schedule A—Construction Sheet (Metals in...

  19. Metal release from stainless steel powders and massive sheets--comparison and implication for risk assessment of alloys.

    PubMed

    Hedberg, Yolanda; Mazinanian, Neda; Odnevall Wallinder, Inger

    2013-02-01

    Industries that place metal and alloy products on the market are required to demonstrate that they are safe for all intended uses, and that any risks to humans, animals or the environment are adequately controlled. This requires reliable and robust in vitro test procedures. The aim of this study is to compare the release of alloy constituents from stainless steel powders of different grades (focus on AISI 316L) and production routes into synthetic body fluids with the release of the same metals from massive sheets in relation to material and surface characteristics. The comparison is justified by the fact that the difference between massive surfaces and powders from a metal release/dissolution and surface perspective is not clearly elucidated within current legislations. Powders and abraded and aged (24 h) massive sheets were exposed to synthetic solutions of relevance for biological settings and human exposure routes, for periods of up to one week. Concentrations of released iron, chromium, nickel, and manganese in solution were measured, and the effect of solution pH, acidity, complexation capacity, and proteins elucidated in relation to surface oxide composition and its properties. Implications for risk assessments based on in vitro metal release data from alloys are elucidated.

  20. Metallic tin quantum sheets confined in graphene toward high-efficiency carbon dioxide electroreduction

    NASA Astrophysics Data System (ADS)

    Lei, Fengcai; Liu, Wei; Sun, Yongfu; Xu, Jiaqi; Liu, Katong; Liang, Liang; Yao, Tao; Pan, Bicai; Wei, Shiqiang; Xie, Yi

    2016-09-01

    Ultrathin metal layers can be highly active carbon dioxide electroreduction catalysts, but may also be prone to oxidation. Here we construct a model of graphene confined ultrathin layers of highly reactive metals, taking the synthetic highly reactive tin quantum sheets confined in graphene as an example. The higher electrochemical active area ensures 9 times larger carbon dioxide adsorption capacity relative to bulk tin, while the highly-conductive graphene favours rate-determining electron transfer from carbon dioxide to its radical anion. The lowered tin-tin coordination numbers, revealed by X-ray absorption fine structure spectroscopy, enable tin quantum sheets confined in graphene to efficiently stabilize the carbon dioxide radical anion, verified by 0.13 volts lowered potential of hydroxyl ion adsorption compared with bulk tin. Hence, the tin quantum sheets confined in graphene show enhanced electrocatalytic activity and stability. This work may provide a promising lead for designing efficient and robust catalysts for electrolytic fuel synthesis.

  1. Sheet Metal Specialist 13-1. Military Curriculum Materials for Vocational and Technical Education.

    ERIC Educational Resources Information Center

    Chanute AFB Technical Training Center, IL.

    This course, adapted from military curriculum materials for use in vocational and technical education, provides training in the theory and practice of sheet metal work. Designed for student self-instruction (such as a correspondence course), the text consists of four volumes. Volume 1 discusses shop mathematics, measurement and layout tools,…

  2. Simulation of sheet-bulk metal forming processes with simufact.forming using user-subroutines

    NASA Astrophysics Data System (ADS)

    Beese, Steffen; Beyer, Florian; Blum, Heribert; Isik, Kerim; Kumor, Dustin; Löhnert, Stefan; Rademacher, Andreas; Tekkaya, A. Erman; Willner, Kai; Wriggers, Peter; Zeller, Sebastian

    2016-10-01

    In this article, we consider the simulation of sheet-bulk metal forming processes, which makes high demands on the underlying models and on the simulation software. We present our approach to incorporate new modelling approaches from various fields in a commercial simulation software, in our case Simufact.forming. Here, we discuss material, damage, and friction models as well as model adaptive techniques.

  3. 75 FR 15741 - Sheet Metal Workers Internationl Association, Local 292: Troy, MI; Notice of Termination of...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-03-30

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF LABOR Employment and Training Administration Sheet Metal Workers Internationl Association, Local 292: Troy, MI... investigation was initiated in response to a petition filed on July 13, 2009 on behalf of workers of Steel...

  4. Widespread complex flow in the interior of the antarctic ice sheet

    PubMed

    Bamber; Vaughan; Joughin

    2000-02-18

    It has been suggested that as much as 90% of the discharge from the Antarctic Ice Sheet is drained through a small number of fast-moving ice streams and outlet glaciers fed by relatively stable and inactive catchment areas. Here, evidence obtained from balance velocity estimates suggests that each major drainage basin is fed by complex systems of tributaries that penetrate up to 1000 kilometers from the grounding line into the interior of the ice sheet. This finding has important consequences for the modeled or estimated dynamic response time of past and present ice sheets to climate forcing.

  5. Fabrication of complex metallic nanostructures by nanoskiving.

    PubMed

    Xu, Qiaobing; Rioux, Robert M; Whitesides, George M

    2007-10-01

    This paper describes the use of nanoskiving to fabricate complex metallic nanostructures by sectioning polymer slabs containing small, embedded metal structures. This method begins with the deposition of thin metallic films on an epoxy substrate by e-beam evaporation or sputtering. After embedding the thin metallic film in an epoxy matrix, sectioning (in a plane perpendicular or parallel to the metal film) with an ultramicrotome generates sections (which can be as thin as 50 nm) of epoxy containing metallic nanostructures. The cross-sectional dimensions of the metal wires embedded in the resulting thin epoxy sections are controlled by the thickness of the evaporated metal film (which can be as small as 20 nm) and the thickness of the sections cut by the ultramicrotome; this work uses a standard 45 degrees diamond knife and routinely generates slabs 50 nm thick. The embedded nanostructures can be transferred to, and positioned on, planar or curved substrates by manipulating the thin polymer film. Removal of the epoxy matrix by etching with an oxygen plasma generates free-standing metallic nanostructures. Nanoskiving can fabricate complex nanostructures that are difficult or impossible to achieve by other methods of nanofabrication. These include multilayer structures, structures on curved surfaces, structures that span gaps, structures in less familiar materials, structures with high aspect ratios, and large-area structures comprising two-dimensional periodic arrays. This paper illustrates one class of application of these nanostructures: frequency-selective surfaces at mid-IR wavelengths.

  6. Luminescent aryl-group eleven metal complexes.

    PubMed

    López-de-Luzuriaga, José M; Monge, Miguel; Olmos, M Elena

    2017-02-14

    Among the coinage metal complexes displaying luminescent properties, those bearing C-donor aryl ligands have an increasing part in the chemistry of these metals. These types of ligands confer a high kinetic and thermodynamic stability on the complexes, but they can also be involved in the photoluminescent behaviour of the complexes. The development of new aryl-containing complexes of group eleven metals, the study of their photoluminescent properties and their related properties and applications are discussed in this perspective. Among these, luminescent gold(i) and gold(iii) compounds are being intensively used for the development of new properties with potential applications such as, for instance, electroluminescence, triboluminescence, mechanochromism, aggregated induced emissions, quenching, luminescent liquid crystals, low molecular weight gelators and photocatalysts, among others.

  7. Characterization and activity of cephalosporin metal complexes.

    PubMed

    Auda, S H; Mrestani, Y; Fetouh, M I; Neubert, R H H

    2008-08-01

    Semi-synthetic cephalosporin antibiotics have structures similar to that of penicillins, and both groups of compounds are characterized by similar properties and determined by the same methods. Most antibiotics, including cephalosporins and their decomposition products, contain electron donor groups that can bind naturally occurring metal ions in vivo. Cephalosporin antibiotics exhibit a change in their toxicological properties and biological performance when they were tested as metal complexes. The proposed reason for such a behavior is the capability of chelate binding of the cephalosporins to the metals. In an attempt to understand the coordination mode of metals with cephalosporins, different spectroscopic techniques such as IR, UV-visible, NMR spectroscopy and voltammetric measurements were carried out to elucidate the structure of the metal-cephalosporin complexes. Synthesis, characterization and biological screening of the cephalosporins and of the cephalosporin-metal complexes are discussed in this review. However, little information is available on the influence of the metal ions on the pharmacokinetics of the cephalosporin derivatives.

  8. Numerical simulations of biaxial experiments on damage and fracture in sheet metal forming

    NASA Astrophysics Data System (ADS)

    Gerke, Steffen; Schmidt, Marco; Brünig, Michael

    2016-08-01

    The damage and failure process of ductile metals is characterized by different mechanisms acting on the micro-scale as well as on the macro-level. These deterioration processes essentially depend on the material type and on the loading conditions. To describe these phenomena in an appropriate way a phenomenological continuum damage and fracture model has been proposed. To detect the effects of stress-state-dependent damage mechanisms, numerical simulations of tests with new biaxial specimen geometries for sheet metals have been performed. The experimental results including digital image correlation (DIC) show good agreement with the corresponding numerical analysis. The presented approach based on both experiments and numerical simulation provides several new aspects in the simulation of sheet metal forming processes.

  9. A Model Based Approach to Increase the Part Accuracy in Robot Based Incremental Sheet Metal Forming

    SciTech Connect

    Meier, Horst; Laurischkat, Roman; Zhu Junhong

    2011-01-17

    One main influence on the dimensional accuracy in robot based incremental sheet metal forming results from the compliance of the involved robot structures. Compared to conventional machine tools the low stiffness of the robot's kinematic results in a significant deviation of the planned tool path and therefore in a shape of insufficient quality. To predict and compensate these deviations offline, a model based approach, consisting of a finite element approach, to simulate the sheet forming, and a multi body system, modeling the compliant robot structure, has been developed. This paper describes the implementation and experimental verification of the multi body system model and its included compensation method.

  10. Three-dimensional reconstruction and morphologic characteristics of porous metal fiber sintered sheet

    SciTech Connect

    Wang, Qinghui; Huang, Xiang; Zhou, Wei; Li, Jingrong

    2013-12-15

    This paper presents an approach to achieve morphological characterizing for complex porous materials based on micro X-ray tomography images, with an example of a novel porous metal fiber sheet produced through solid-state sintering method. The geometrical reconstruction was performed after selection of volume of interest and image processing of anisotropic diffusion smooth. The reconstructed gray level images were then transferred into binary images by adjusting binarization threshold according to the actual porosity. Taking into account the tubular structural feature of the fibers, skeleton extraction algorithm based on the distance transform function was applied and further improved by the scale axis transform method. The skeleton was later pruned and segmented according to the contact points to perform morphological characterizing. Compared with actual manufacturing parameters, the style, length, radius, orientation and tortuosity of fiber segments were discussed. The results show that our proposed method can well describe the actual geometrical and morphological characteristics, which will provide a promising method for the structural description of fibrous networks. - Highlights: • Micro-CT technology was used to achieve the 3D geometrical reconstruction. • Skeleton extraction algorithm was modified to get the medial skeleton. • Skeleton filter operation was adopted to deal with the segmented skeleton. • Useful morphological statistics was obtained through skeleton segments. • Relationship between structure and manufacturing processes was discussed.

  11. On the role of topological complexity in spontaneous development of current sheets

    SciTech Connect

    Kumar, Sanjay; Bhattacharyya, R.; Smolarkiewicz, P. K.

    2015-08-15

    The computations presented in this work aim to asses the importance of field line interlacing on spontaneous development of current sheets. From Parker's magnetostatic theorem, such development of current sheets is inevitable in a topologically complex magnetofluid, with infinite electrical conductivity, at equilibrium. Relevant initial value problems are constructed by superposition of two untwisted component fields, each component field being represented by a pair of global magnetic flux surface. The intensity of field line interlacing is then specified by the relative amplitude of the two superposed fields. The computations are performed by varying this relative amplitude. Also to have a direct visualization of current sheet formation, we follow the evolution of flux surfaces instead of the vector magnetic field. An important finding of this paper is in the demonstration that initial field lines having intense interlacing tend to develop current sheets which are distributed throughout the computational domain with no preference for topologically favorable sites like magnetic nulls or field reversal layers. The onsets of these current sheets are attributed to favorable contortions of magnetic flux surfaces where two oppositely directed parts of the same field line or different field lines come to close proximity. However, for less intensely interlaced field lines, the simulations indicate development of current sheets at sites only where the magnetic topology is favorable. These current sheets originate as two sets of anti-parallel complimentary field lines press onto each other.

  12. Sheet metal stamping die design for warm forming

    DOEpatents

    Ghosh, Amit K.

    2003-04-22

    In metal stamping dies, by taking advantage of improved material flow by selectively warming the die, flat sections of the die can contribute to the flow of material throughout the workpiece. Local surface heating can be accomplished by placing a heating block in the die. Distribution of heating at the flat lower train central regions outside of the bend region allows a softer flow at a lower stress to enable material flow into the thinner, higher strain areas at the bend/s. The heating block is inserted into the die and is powered by a power supply.

  13. Studies on the finite element simulation in sheet metal stamping processes

    NASA Astrophysics Data System (ADS)

    Huang, Ying

    The sheet metal stamping process plays an important role in modern industry. With the ever-increasing demand for shape complexity, product quality and new materials, the traditional trial and error method for setting up a sheet metal stamping process is no longer efficient. As a result, the Finite Element Modeling (FEM) method has now been widely used. From a physical point of view, the formability and the quality of a product are influenced by several factors. The design of the product in the initial stage and the motion of the press during the production stage are two of these crucial factors. This thesis focuses on the numerical simulation for these two factors using FEM. Currently, there are a number of commercial FEM software systems available in the market. These software systems are based on an incremental FEM process that models the sheet metal stamping process in small incremental steps. Even though the incremental FEM is accurate, it is not suitable for the initial conceptual design for its needing of detailed design parameters and enormous calculation times. As a result, another type of FEM, called the inverse FEM method or one-step FEM method, has been proposed. While it is less accurate than that of the incremental method, this method requires much less computation and hence, has a great potential. However, it also faces a number of unsolved problems, which limits its application. This motivates the presented research. After the review of the basic theory of the inverse method, a new modified arc-length search method is proposed to find better initial solution. The methods to deal with the vertical walls are also discussed and presented. Then, a generalized multi-step inverse FEM method is proposed. It solves two key obstacles: the first one is to determine the initial solution of the intermediate three-dimensional configurations and the other is to control the movement of nodes so they could only slide on constraint surfaces during the search by

  14. Novel metals and metal complexes as platforms for cancer therapy.

    PubMed

    Frezza, Michael; Hindo, Sarmad; Chen, Di; Davenport, Andrew; Schmitt, Sara; Tomco, Dajena; Dou, Q Ping

    2010-06-01

    Metals are essential cellular components selected by nature to function in several indispensable biochemical processes for living organisms. Metals are endowed with unique characteristics that include redox activity, variable coordination modes, and reactivity towards organic substrates. Due to their reactivity, metals are tightly regulated under normal conditions and aberrant metal ion concentrations are associated with various pathological disorders, including cancer. For these reasons, coordination complexes, either as drugs or prodrugs, become very attractive probes as potential anticancer agents. The use of metals and their salts for medicinal purposes, from iatrochemistry to modern day, has been present throughout human history. The discovery of cisplatin, cis-[Pt(II) (NH(3))(2)Cl(2)], was a defining moment which triggered the interest in platinum(II)- and other metal-containing complexes as potential novel anticancer drugs. Other interests in this field address concerns for uptake, toxicity, and resistance to metallodrugs. This review article highlights selected metals that have gained considerable interest in both the development and the treatment of cancer. For example, copper is enriched in various human cancer tissues and is a co-factor essential for tumor angiogenesis processes. However the use of copper-binding ligands to target tumor copper could provide a novel strategy for cancer selective treatment. The use of nonessential metals as probes to target molecular pathways as anticancer agents is also emphasized. Finally, based on the interface between molecular biology and bioinorganic chemistry the design of coordination complexes for cancer treatment is reviewed and design strategies and mechanisms of action are discussed.

  15. Metal Complexes for Defense against Cyanide Intoxication

    DTIC Science & Technology

    1986-11-01

    cyanide toxicity might be compared with that of other asphyxiants, particularly carbon monoxide. Carbon monoxide forms a complex with hemoglobin... carbon monoxide is present to disrupt the oxygen transport to the tissue. However, cyanide is toxic at much lower concentrations. According to ligand... carbon to an empty d-orbital on the metal, plus a it-bond, which is formed by the back-donation of a filled metal d-orbital to the empty antibonding

  16. Corrosion evaluation of coated sheet metal by means of thermography and image analysis

    NASA Astrophysics Data System (ADS)

    Jernberg, Per

    1991-03-01

    The fact that organic binders, as used in paints, are transparent in the IR range 3.5-5.5 microns is utilized to detect and measure defects under the paint film of sheet metals. However, the method demands an elevated sample temperature to suppress reflections from the surrounding and is till now resorted to laboratory investigations. The IR system used is an AGEMA Thermovision 880 SWB. The maximum thickness of the paint film allowing evaluation is mainly governed by the absorption and the refraction caused by the paint pigments, depending upon pigment size and pigment material. To be detectable the defects have to be characterized by IR emissivities considerably different from the emissivity of the bare sheet metal as is found for metallic corrosion products. A quantitative determination of a corrosion attack is obtained by evaluating the IR image at a PC based image analyzer. As a standard today, such evaluations are performed by inspecting and comparing painted sheet metals with reference photographs. This method suffers both from the subjectiveness of the observer and the opaqueness of the paint film in the visible range.

  17. Special issue: practical applications of metal complexes.

    PubMed

    Turel, Iztok

    2015-04-30

    In 1913 Alfred Werner received the Nobel Prize in Chemistry for his work that was of great importance for the development of coordination chemistry. In the years that followed numerous complexes consisting of metal ions and organic ligands were isolated, thus building a strong connection between inorganic and organic chemistry. Coordination compounds have many interesting properties which find diverse applications in numerous aspects of human life. Fourteeen contributions were received for this Special Issue covering very different aspects of metal complexes and their practical applications. The highest number of manuscripts deals with the biological activity of complexes which might potentially be used in the clinical practice. Authors have tested their cytotoxicity, antibacterial activity and enzyme inhibition. Their optical properties were studied in view of their potential use in photodynamic therapy. Moreover, optical properties could also be used for bioanalysis. It is also known that metal complexes are useful catalysts and a few such examples are also described herein. Many other interesting properties and facts about the isolated and described complexes are also reported (radioactivity, design of metal-organic frameworks, etc.).

  18. A New System for Understanding Mid-crustal Sheeted Complexes in a Tilted Crustal Section, Joshua Tree National Park, California

    NASA Astrophysics Data System (ADS)

    Ianno, A. J.; Paterson, S. R.

    2011-12-01

    The western portion of Joshua Tree National Park exposes a tilted crustal section through continental arc crust from 0-30 km. A significant portion of the middle crust is represented by Mesozoic, tabular, intrusive, igneous bodies ranging from 0.1 to 100 m in thickness. While these igneous bodies range in composition (gabbro to peraluminous granites), texture (equigranular to porphyritic), and grain size (very fine to coarse), patterns emerge between different regions of "sheeted complexes" that may be related to their emplacement and geochemical history. No consistent method of describing and comparing sheeted complexes exists in the literature, so we have developed a method of classifying sheeted complexes at Joshua Tree NP, which may be broadly applicable to all sheeted bodies. We classify these sheeted complexes using the terms homogeneous/heterogeneous and focused/defocused. A homogeneous sheeted complex generally contains magmas within a 10 wt% SiO2 range, although we are still testing the validity of this number. A focused sheeted complex has adjacent sheets or close spacing between sheets and <20% host rock present. Using this classification scheme, we observe three distinct Jurassic to Cretaceous sheeted complexes in western Joshua Tree NP. At Keys View, we observe a heterogeneous, spatially focused sheeted complex with 0.1-2 m thick sheets recording pressures indicating 15-22 km depth from top to bottom. Compositions range from gabbro to peraluminous granite, although tonalites-granodiorites and two-mica garnet granites are volumetrically dominant. A zone of elongate plutons (in map view) lying structurally above this could potentially be considered as a very thickly sheeted, homogeneous, focused sheeted complex and is composed of granodiorites, granites, and two-mica garnet granites. A more thickly sheeted (2-10 m), homogeneous, focused, sheeted granite complex with pressures indicating a depth of approximately 12 km is found along the northern edge of

  19. Failure Analysis of a Sheet Metal Blanking Process Based on Damage Coupling Model

    NASA Astrophysics Data System (ADS)

    Wen, Y.; Chen, Z. H.; Zang, Y.

    2013-11-01

    In this paper, a blanking process of sheet metal is studied by the methods of numerical simulation and experimental observation. The effects of varying technological parameters related to the quality of products are investigated. An elastoplastic constitutive equation accounting for isotropic ductile damage is implemented into the finite element code ABAQUS with a user-defined material subroutine UMAT. The simulations of the damage evolution and ductile fracture in a sheet metal blanking process have been carried out by the FEM. In order to guarantee computation accuracy and avoid numerical divergence during large plastic deformation, a specified remeshing technique is successively applied when severe element distortion occurs. In the simulation, the evolutions of damage at different stage of the blanking process have been evaluated and the distributions of damage obtained from simulation are in proper agreement with the experimental results.

  20. Friction and lubrication modeling in sheet metal forming simulations of a Volvo XC90 inner door

    NASA Astrophysics Data System (ADS)

    Sigvant, M.; Pilthammar, J.; Hol, J.; Wiebenga, J. H.; Chezan, T.; Carleer, B.; van den Boogaard, A. H.

    2016-11-01

    The quality of sheet metal formed parts is strongly dependent on the tribology, friction and lubrication conditions that are acting in the actual production process. Although friction is of key importance, it is currently not considered in detail in stamping simulations. This paper presents a selection of results considering friction and lubrication modeling in sheet metal forming simulations of the Volvo XC90 right rear door inner. For this purpose, the TriboForm software is used in combination with the AutoForm software. Validation of the simulation results is performed using door inner parts taken from the press line in a full-scale production run. The results demonstrate the improved prediction accuracy of stamping simulations by accounting for accurate friction and lubrication conditions, and the strong influence of friction conditions on both the part quality and the overall production stability.

  1. Advanced finite element analysis of die wear in sheet-bulk metal forming processes

    NASA Astrophysics Data System (ADS)

    Behrens, Bernd-Arno; Bouguecha, Anas; Vucetic, Milan; Chugreev, Alexander; Rosenbusch, Daniel

    2016-10-01

    The novel sheet-bulk metal forming (SBMF) technology allows the production of solid metal components with various functional design features out of flat sheet specimens. However, due to the high working pressures arising during the forming process the efficiency of SBMF is tightly related to the tool service life, which is mainly limited by die wear. In the forming processes involving high contact pressures (e.g. SBMF) the influence of contact normal stresses on the die wear can be overestimated. In order to provide a realistic estimation of the die wear, the shear friction stress must be considered. The presented paper introduces a die wear model that intends the tangential component of contact stress and its implementation in the commercial FE code.

  2. Trimming Simulation of Forming Metal Sheets Isogeometric Models by Using NURBS Surfaces

    NASA Astrophysics Data System (ADS)

    Herrero-Adan, D.; Cardoso, Rui P. R.; Adetoro, O. B.

    2016-08-01

    Some metal sheets forming processes need trimming in a final stage for achieving the net- shape specification and for removing micro-cracks and irregularities. In numerical simulation, since the exact final edge location is a priori unknown in the original metal blanket, the trimming needs to be done once the forming is finished. During the forming internal stresses are generated inside the sheet. When trimming those stresses configuration is changed to achieve equilibrium as a consequence of the material removal. In this paper a novel method for simulating the trimming is presented. The part to trim is modelled using isogeometric analysis (IGA). The new surface generated is modelled with non-uniform rational B-splines (NURBS). Due to the IGA characteristics a total geometrical accuracy and an efficient residual stresses recalculation are accomplished.

  3. Biomimetic cavity-based metal complexes.

    PubMed

    Rebilly, Jean-Noël; Colasson, Benoit; Bistri, Olivia; Over, Diana; Reinaud, Olivia

    2015-01-21

    The design of biomimetic complexes for the modeling of metallo-enzyme active sites is a fruitful strategy for obtaining fundamental information and a better understanding of the molecular mechanisms at work in Nature's chemistry. The classical strategy for modeling metallo-sites relies on the synthesis of metal complexes with polydentate ligands that mimic the coordination environment encountered in the natural systems. However, it is well recognized that metal ion embedment in the proteic cavity has key roles not only in the recognition events but also in generating transient species and directing their reactivity. Hence, this review focuses on an important aspect common to enzymes, which is the presence of a pocket surrounding the metal ion reactive sites. Through selected examples, the following points are stressed: (i) the design of biomimetic cavity-based complexes, (ii) their corresponding host-guest chemistry, with a special focus on problems related to orientation and exchange mechanisms of the ligand within the host, (iii) cavity effects on the metal ion binding properties, including 1st, 2nd, and 3rd coordination spheres and hydrophobic effects and finally (iv) the impact these factors have on the reactivity of embedded metal ions. Important perspectives lie in the use of this knowledge for the development of selective and sensitive probes, new reactions, and green and efficient catalysts with bio-inspired systems.

  4. Finite element simulation of sheet metal forming and springback using a crystal plasticity approach

    SciTech Connect

    Bertram, A.; Boehlke, T.; Krawietz, A.; Schulze, V.

    2007-05-17

    In this paper the application of a crystal plasticity model for body-centered cubic crystals in the simulation of a sheet metal forming process is discussed. The material model parameters are identified by a combination of a texture approximation procedure and a conventional parameter identification scheme. In the application of a cup drawing process the model shows an improvement of the strain and earing prediction as well as the qualitative springback results in comparison with a conventional phenomenological model.

  5. Matched metal die compression molded structural random fiber sheet molding compound flywheel

    DOEpatents

    Kulkarni, Satish V.; Christensen, Richard M.; Toland, Richard H.

    1985-01-01

    A flywheel (10) is described that is useful for energy storage in a hybrid vehicle automotive power system or in some stationary applications. The flywheel (10) has a body of essentially planar isotropic high strength structural random fiber sheet molding compound (SMC-R). The flywheel (10) may be economically produced by a matched metal die compression molding process. The flywheel (10) makes energy intensive efficient use of a fiber/resin composite while having a shape designed by theory assuming planar isotropy.

  6. Matched metal die compression molded structural random fiber sheet molding compound flywheel. [Patent application

    DOEpatents

    Kulkarni, S.V.; Christensen, R.M.; Toland, R.H.

    1980-09-24

    A flywheel is described that is useful for energy storage in a hybrid vehicle automotive power system or in some stationary applications. The flywheel has a body of essentially planar isotropic high strength structural random fiber sheet molding compound (SMC-R). The flywheel may be economically produced by a matched metal die compression molding process. The flywheel makes energy intensive efficient use of a fiber/resin composite while having a shape designed by theory assuming planar isotropy.

  7. Alkene epoxidation employing metal nitro complexes

    DOEpatents

    Andrews, M.A.; Cheng, C.W.; Kelley, K.P.

    1982-07-15

    Process for converting alkenes to form epoxides utilizes transition metal nitro complexes of the formula: M(RCN)/sub 2/XNO/sub 2/ wherein M is palladium or platinum, R is an alkyl or aryl group containing up to 12 carbon atoms, and X is a monoanionic, monodentate ligand such as chlorine, optionally in the presence of molecular oxygen.

  8. Research on precision control of sheet metal forming by laser shock waves with semi-die

    NASA Astrophysics Data System (ADS)

    Jiang, Yinfang; Huang, Yu; Jin, Hua; Gu, Yongyu; Ren, Aiguo; Huang, Liwei; Qian, Xiaoming

    2013-02-01

    Laser shock forming is a new technique which enables sheet metal to produce plastic deformation through shock waves induced by high energy pulsed laser. However, it is difficult to control the forming precision with such technique. This paper provided the kinetic analysis of sheet metal during the progress of laser shock forming with semi-die. It also developed the method of forming precision control with optimal laser pulse energy, method of die modification and compensation based on reverse analysis and method of characterizing the precision of laser shock forming with semi-die. The Nd:Glass pulse laser was used in the laser shock semi-die forming experiment of constant elastic alloy 3J53 sheet metal. The experiment results show that the optimal laser pulse energy of precision control in laser shock semi-die forming is 15 J; and forming error can be reduced by more than 50% with the method of contours modification and compensation. The research work also lays a foundation for the theory formation of precision control of laser shock semi-die forming and the engineering applications of the laser shock forming technique.

  9. Analysis of Dynamic Loads on the Dies in High Speed Sheet Metal Forming Processes

    NASA Astrophysics Data System (ADS)

    Ibrahim, R.; Golovashchenko, S.; Smith, L. M.; Mamutov, A.; Bonnen, J.; Gillard, A.

    2014-05-01

    During high-speed sheet metal forming processes, the speed at which the work piece contacts the die tooling is on the order of hundreds of meters per second. When the impact is concentrated over a small contact area, the resulting contact stress can compromise the structural integrity of the die tooling. Therefore, it is not only important to model the behavior of the workpiece during the high-speed sheet metal forming process, but also important to predict accurately the associated workpiece/tooling interface loads so that engineers can more confidently propose robust die tooling designs. The foundation to accurate predictions of contact stress on die tooling is a reliable contact model within the context of a finite element simulation. In literature, however, there exists no comprehensive guideline for establishing a contact model for high-speed sheet metal forming processes using the finite element method. In this paper, mathematically justified contact model recommendations are offered for the electrohydraulic forming (EHF) process.

  10. NREL's System Advisor Model Simplifies Complex Energy Analysis (Fact Sheet)

    SciTech Connect

    Not Available

    2011-10-01

    The energy market is diversifying. In addition to traditional power sources, decision makers can choose among solar, wind, and geothermal technologies as well. Each of these technologies has complex performance characteristics and economics that vary with location and other project specifics, making it difficult to analyze the viability of such projects. But that analysis is easier now, thanks to the National Renewable Energy Laboratory (NREL).

  11. Coherent states on the m-sheeted complex plane as m-photon states

    NASA Technical Reports Server (NTRS)

    Vourdas, Apostolos

    1994-01-01

    Coherent states on the m-sheeted complex plane are introduced and properties like overcompleteness and resolution of the identity are studied. They are eigenstates of the operators a(sub m)(+), a(sub m) which create and annihilate clusters of m-particles. Applications of this formalism in the study of Hamiltonians that describe m-particle clustering are also considered.

  12. Anharmonic Vibrational Spectroscopy on Metal Transition Complexes

    NASA Astrophysics Data System (ADS)

    Latouche, Camille; Bloino, Julien; Barone, Vincenzo

    2014-06-01

    Advances in hardware performance and the availability of efficient and reliable computational models have made possible the application of computational spectroscopy to ever larger molecular systems. The systematic interpretation of experimental data and the full characterization of complex molecules can then be facilitated. Focusing on vibrational spectroscopy, several approaches have been proposed to simulate spectra beyond the double harmonic approximation, so that more details become available. However, a routine use of such tools requires the preliminary definition of a valid protocol with the most appropriate combination of electronic structure and nuclear calculation models. Several benchmark of anharmonic calculations frequency have been realized on organic molecules. Nevertheless, benchmarks of organometallics or inorganic metal complexes at this level are strongly lacking despite the interest of these systems due to their strong emission and vibrational properties. Herein we report the benchmark study realized with anharmonic calculations on simple metal complexes, along with some pilot applications on systems of direct technological or biological interest.

  13. Final Air Toxics Standards for Clay Ceramics Manufacturing, Glass Manufacturing, and Secondary Nonferrous Metals Processing Area Sources Fact Sheet

    EPA Pesticide Factsheets

    This page contains a December 2007 fact sheet with information regarding the National Emissions Standards for Hazardous Air Pollutants (NESHAP) for Clay Ceramics Manufacturing, Glass Manufacturing, and Secondary Nonferrous Metals Processing Area Sources

  14. Observed use of voluntary controls to reduce physical exposures among sheet metal workers of the mechanical trade

    PubMed Central

    Dale, Ann Marie; Miller, Kim; Gardner, Bethany T.; Hwang, Ching-Ting; Evanoff, Bradley; Welch, Laura

    2015-01-01

    Introduction Little is known about the transfer into the workplace of interventions designed to reduce the physical demands of sheet metal workers. Methods We reviewed videos from a case series of 15 sheet metal worksite assessments performed in 2007–2009 to score postures and physical loads, and to observe the use of recommended interventions to reduce physical exposures in sheet metal activities made by a NIOSH stakeholder meeting in 2002. Results Workers showed consistent use of material handling devices, but we observed few uses of recommended interventions to reduce exposures during overhead work. Workers spent large proportions of time in awkward shoulder elevation and low back rotation postures. Conclusions In addition to the development of new technologies and system designs, increased adoption of existing tools and practices could reduce time spent in awkward postures and other risks for musculoskeletal disorders in sheet metal work. PMID:26360196

  15. Fact Sheet: Final Rule to Reduce Toxic Air Pollutants from Surface Coating of Miscellaneous Metal Parts and Products

    EPA Pesticide Factsheets

    This page contains an August 2003 fact sheet with information regarding the National Emission Standards for Miscellaneous Metal Parts and Products Surface Coating Operations. This document provides a summary of the information for this regulation.

  16. Development of a Prediction Model Based on RBF Neural Network for Sheet Metal Fixture Locating Layout Design and Optimization.

    PubMed

    Wang, Zhongqi; Yang, Bo; Kang, Yonggang; Yang, Yuan

    2016-01-01

    Fixture plays an important part in constraining excessive sheet metal part deformation at machining, assembly, and measuring stages during the whole manufacturing process. However, it is still a difficult and nontrivial task to design and optimize sheet metal fixture locating layout at present because there is always no direct and explicit expression describing sheet metal fixture locating layout and responding deformation. To that end, an RBF neural network prediction model is proposed in this paper to assist design and optimization of sheet metal fixture locating layout. The RBF neural network model is constructed by training data set selected by uniform sampling and finite element simulation analysis. Finally, a case study is conducted to verify the proposed method.

  17. CrachFEM - A Comprehensive Approach For The Prediction Of Sheet Metal Failure

    SciTech Connect

    Dell, Harry; Gese, Helmut; Oberhofer, Gernot

    2007-05-17

    A correct prediction of a possible sheet metal failure is essential to sheet metal forming simulations. The use of the conventional forming limit curve (FLC) is the standard approach on industrial level for this problem. The FLC concept is limited to the case of linear strain paths, however. The initial FLC is no longer valid in the case of nonlinear strain paths. The algorithm Crach allows for a transient prediction of the forming limit for localized necking in the case of arbitrary strain paths. For high strength steels and aluminium sheets there is also a risk of fracture without prior localized necking. This paper presents a fracture model that accounts for ductile fracture (caused by void nucleation, void growth and void coalescence) and shear fracture (caused by shear band localization). For both types of fracture, stress state parameters are introduced which can be applied for the plane stress state and for the general 3D stress state. The fracture limits are defined by the equivalent plastic strain at fracture as a function of the stress state parameter based on different experiments with nearly constant stress state parameter. These fracture limit curves are a basis for an integral damage accumulation in the sheet metal forming simulation for arbitrary nonlinear strain paths. The model Crach for the prediction of localized necking and the two fracture models for ductile and shear fracture are combined in the comprehensive failure model CrachFEM. CrachFEM can be linked via a user material model MF GenYld to different explicit FEM codes.

  18. Possibilities And Influencing Parameters For The Early Detection Of Sheet Metal Failure In Press Shop Operations

    NASA Astrophysics Data System (ADS)

    Gerlach, Jörg; Kessler, Lutz; Paul, Udo; Rösen, Hartwig

    2007-05-01

    The concept of forming limit curves (FLC) is widely used in industrial practice. The required data should be delivered for typical material properties (measured on coils with properties in a range of +/- of the standard deviation from the mean production values) by the material suppliers. In particular it should be noted that its use for the validation of forming robustness providing forming limit curves for the variety of scattering in the mechanical properties is impossible. Therefore a forecast of the expected limit strains without expensive cost and time-consuming experiments is necessary. In the paper the quality of a regression analysis for determining forming limit curves based on tensile test results is presented and discussed. Owing to the specific definition of limit strains with FLCs following linear strain paths, the significance of this failure definition is limited. To consider nonlinear strain path effects, different methods are given in literature. One simple method is the concept of limit stresses. It should be noted that the determined value of the critical stress is dependent on the extrapolation of the tensile test curve. When the yield curve extrapolation is very similar to an exponential function, the definition of the critical stress value is very complicated due to the low slope of the hardening function at large strains. A new method to determine general failure behavior in sheet metal forming is the common use and interpretation of three criteria: onset on material instability (comparable with FLC concept), value of critical shear fracture and the value of ductile fracture. This method seems to be particularly successful for newly developed high strength steel grades in connection with more complex strain paths for some specific material elements. Nevertheless the identification of the different failure material parameters or functions will increase and the user has to learn with the interpretation of the numerical results.

  19. Metal-Metal Bonding in Uranium-Group 10 Complexes.

    PubMed

    Hlina, Johann A; Pankhurst, James R; Kaltsoyannis, Nikolas; Arnold, Polly L

    2016-03-16

    Heterobimetallic complexes containing short uranium-group 10 metal bonds have been prepared from monometallic IU(IV)(OAr(P)-κ(2)O,P)3 (2) {[Ar(P)O](-) = 2-tert-butyl-4-methyl-6-(diphenylphosphino)phenolate}. The U-M bond in IU(IV)(μ-OAr(P)-1κ(1)O,2κ(1)P)3M(0), M = Ni (3-Ni), Pd (3-Pd), and Pt (3-Pt), has been investigated by experimental and DFT computational methods. Comparisons of 3-Ni with two further U-Ni complexes XU(IV)(μ-OAr(P)-1κ(1)O,2κ(1)P)3Ni(0), X = Me3SiO (4) and F (5), was also possible via iodide substitution. All complexes were characterized by variable-temperature NMR spectroscopy, electrochemistry, and single crystal X-ray diffraction. The U-M bonds are significantly shorter than any other crystallographically characterized d-f-block bimetallic, even though the ligand flexes to allow a variable U-M separation. Excellent agreement is found between the experimental and computed structures for 3-Ni and 3-Pd. Natural population analysis and natural localized molecular orbital (NLMO) compositions indicate that U employs both 5f and 6d orbitals in covalent bonding to a significant extent. Quantum theory of atoms-in-molecules analysis reveals U-M bond critical point properties typical of metallic bonding and a larger delocalization index (bond order) for the less polar U-Ni bond than U-Pd. Electrochemical studies agree with the computational analyses and the X-ray structural data for the U-X adducts 3-Ni, 4, and 5. The data show a trend in uranium-metal bond strength that decreases from 3-Ni down to 3-Pt and suggest that exchanging the iodide for a fluoride strengthens the metal-metal bond. Despite short U-TM (transition metal) distances, four other computational approaches also suggest low U-TM bond orders, reflecting highly transition metal localized valence NLMOs. These are more so for 3-Pd than 3-Ni, consistent with slightly larger U-TM bond orders in the latter. Computational studies of the model systems (PH3)3MU(OH)3I (M = Ni, Pd) reveal

  20. Validation of formability of laminated sheet metal for deep drawing process using GTN damage model

    SciTech Connect

    Lim, Yongbin; Cha, Wan-gi; Kim, Naksoo; Ko, Sangjin

    2013-12-16

    In this study, we studied formability of PET/PVC laminated sheet metal which named VCM (Vinyl Coated Metal). VCM offers various patterns and good-looking metal steel used for appliances such as refrigerator and washing machine. But, this sheet has problems which are crack and peeling of film when the material is formed by deep drawing process. To predict the problems, we used finite element method and GTN (Gurson-Tvergaard-Needleman) damage model to represent damage of material. We divided the VCM into 3 layers (PET film, adhesive and steel added PVC) in finite element analysis model to express the crack and peeling phenomenon. The material properties of each layer are determined by reverse engineering based on tensile test result. Furthermore, we performed the simple rectangular deep drawing and simulated it. The simulation result shows good agreement with drawing experiment result in position, punch stroke of crack occurrence. Also, we studied the fracture mechanism of PET film on VCM by comparing the width direction strain of metal and PET film.

  1. Validation of formability of laminated sheet metal for deep drawing process using GTN damage model

    NASA Astrophysics Data System (ADS)

    Lim, Yongbin; Cha, Wan-gi; Ko, Sangjin; Kim, Naksoo

    2013-12-01

    In this study, we studied formability of PET/PVC laminated sheet metal which named VCM (Vinyl Coated Metal). VCM offers various patterns and good-looking metal steel used for appliances such as refrigerator and washing machine. But, this sheet has problems which are crack and peeling of film when the material is formed by deep drawing process. To predict the problems, we used finite element method and GTN (Gurson-Tvergaard-Needleman) damage model to represent damage of material. We divided the VCM into 3 layers (PET film, adhesive and steel added PVC) in finite element analysis model to express the crack and peeling phenomenon. The material properties of each layer are determined by reverse engineering based on tensile test result. Furthermore, we performed the simple rectangular deep drawing and simulated it. The simulation result shows good agreement with drawing experiment result in position, punch stroke of crack occurrence. Also, we studied the fracture mechanism of PET film on VCM by comparing the width direction strain of metal and PET film.

  2. Metallic tin quantum sheets confined in graphene toward high-efficiency carbon dioxide electroreduction

    PubMed Central

    Lei, Fengcai; Liu, Wei; Sun, Yongfu; Xu, Jiaqi; Liu, Katong; Liang, Liang; Yao, Tao; Pan, Bicai; Wei, Shiqiang; Xie, Yi

    2016-01-01

    Ultrathin metal layers can be highly active carbon dioxide electroreduction catalysts, but may also be prone to oxidation. Here we construct a model of graphene confined ultrathin layers of highly reactive metals, taking the synthetic highly reactive tin quantum sheets confined in graphene as an example. The higher electrochemical active area ensures 9 times larger carbon dioxide adsorption capacity relative to bulk tin, while the highly-conductive graphene favours rate-determining electron transfer from carbon dioxide to its radical anion. The lowered tin–tin coordination numbers, revealed by X-ray absorption fine structure spectroscopy, enable tin quantum sheets confined in graphene to efficiently stabilize the carbon dioxide radical anion, verified by 0.13 volts lowered potential of hydroxyl ion adsorption compared with bulk tin. Hence, the tin quantum sheets confined in graphene show enhanced electrocatalytic activity and stability. This work may provide a promising lead for designing efficient and robust catalysts for electrolytic fuel synthesis. PMID:27585984

  3. Calibration of Gurson-type models for porous sheet metals with anisotropic non-quadratic plasticity

    NASA Astrophysics Data System (ADS)

    Gologanu, M.; Kami, A.; Comsa, D. S.; Banabic, D.

    2016-08-01

    The growth and coalescence of voids in sheet metals are not only the main active mechanisms in the final stages of fracture in a necking band, but they also contribute to the forming limits via changes in the normal directions to the yield surface. A widely accepted method to include void effects is the development of a Gurson-type model for the appropriate yield criterion, based on an approximate limit analysis of a unit cell containing a single spherical, spheroidal or ellipsoidal void. We have recently [2] obtained dissipation functions and Gurson-type models for porous sheet metals with ellipsoidal voids and anisotropic non-quadratic plasticity, including yield criteria based on linear transformations (Yld91 and Yld2004-18p) and a pure plane stress yield criteria (BBC2005). These Gurson-type models contain several parameters that depend on the void and cell geometries and on the selected yield criterion. Best results are obtained when these key parameters are calibrated via numerical simulations using the same unit cell and a few representative loading conditions. The single most important such loading condition corresponds to a pure hydrostatic macroscopic stress (pure pressure) and the corresponding velocity field found during the solution of the limit analysis problem describes the expansion of the cavity. However, for the case of sheet metals, the condition of plane stress precludes macroscopic stresses with large triaxiality or ratio of mean stress to equivalent stress, including the pure hydrostatic case. Also, pure plane stress yield criteria like BBC2005 must first be extended to 3D stresses before attempting to develop a Gurson-type model and such extensions are purely phenomenological with no due account for the out- of-plane anisotropic properties of the sheet. Therefore, we propose a new calibration method for Gurson- type models that uses only boundary conditions compatible with the plane stress requirement. For each such boundary condition we use

  4. Direct Imaging of Single Plasmonic Metal Nanoparticles in Capillary with Laser Light-Sheet Scattering Imaging.

    PubMed

    Cao, Xuan; Feng, Jingjing; Pan, Qi; Xiong, Bin; He, Yan; Yeung, Edward S

    2017-03-07

    Understanding the heterogeneous distribution of the physical and chemical properties of plasmonic metal nanoparticles is fundamentally important to their basic and applied research. Traditionally, they are obtained either indirectly via bulk spectroscopic measurements plus electron microscopic characterizations or through single molecule/particle imaging of nanoparticles immobilized on planar substrates. In this study, by using light-sheet scattering microscopy with a supercontinuum white laser, highly sensitive imaging of individual metal nanoparticles (MNPs) flowing inside a capillary, driven by either pressure or electric field, was achieved for the first time. We demonstrate that single plasmonic nanoparticles with different size or chemical modification could be differentiated through their electrophoretic mobility in a few minutes. This technique could potentially be applied to high throughput characterization and evaluation of single metal nanoparticles as well as their dynamic interactions with various local environments.

  5. Forming Limits in Sheet Metal Forming for Non-Proportional Loading Conditions - Experimental and Theoretical Approach

    SciTech Connect

    Ofenheimer, Aldo; Buchmayr, Bruno; Kolleck, Ralf

    2005-08-05

    The influence of strain paths (loading history) on material formability is well known in sheet forming processes. Sophisticated experimental methods are used to determine the entire shape of strain paths of forming limits for aluminum AA6016-T4 alloy. Forming limits for sheet metal in as-received condition as well as for different pre-deformation are presented. A theoretical approach based on Arrieux's intrinsic Forming Limit Stress Curve (FLSC) concept is employed to numerically predict the influence of loading history on forming severity. The detailed experimental strain paths are used in the theoretical study instead of any linear or bilinear simplified loading histories to demonstrate the predictive quality of forming limits in the state of stress.

  6. Angular dependence of the ultrasonic SH wave velocity in rolled metal sheets

    NASA Astrophysics Data System (ADS)

    Sayers, C. M.; Proudfoot, G. G.

    THE ULTRASONIC SH wave technique is a promising method for separating out the effects of texture and stress on the ultrasonic velocity, and allows the texture and stress to be determined separately. ALEN and LANGMAN (1985) have reported measurements of the angular dependence of the SH wave velocity in several unstressed rolled metal sheets of aluminium, stainless steel, copper and brass. In this paper neutron diffraction measurements of the texture of several of these sheets are presented, and parameters entering into an expansion of the crystallite orientation distribution function are determined. These are in good agreement with the values obtained by fitting the ultrasonic results to theory. The validity of the first order expression for the effect of texture is assessed, and the contribution due to beam skewing is calculated.

  7. Simulation of cylindrical cup drawing of AZ31 sheet metal with crystal plasticity finite element method

    NASA Astrophysics Data System (ADS)

    Tang, Weiqin; Li, Dayong; Zhang, Shaorui; Peng, Yinghong

    2013-12-01

    As a light-weight structural material, magnesium alloys show good potential in improving the fuel efficiency of vehicles and reducing CO2 emissions. However, it is well known that polycrystalline Mg alloys develop pronounced crystallographic texture and plastic anisotropy during rolling, which leads to earing phenomenon during deep drawing of the rolled sheets. It is vital to predict this phenomenon accurately for application of magnesium sheet metals. In the present study, a crystal plasticity model for AZ31 magnesium alloy that incorporates both slip and twinning is established. Then the crystal plasticity model is implemented in the commercial finite element software ABAQUS/Explicit through secondary development interface (VUMAT). Finally, the stamping process of a cylindrical cup is simulated using the developed crystal plasticity finite element model, and the predicting method is verified by comparing with experimental results from both earing profile and deformation texture.

  8. Topometry optimization of sheet metal structures for crashworthiness design using hybrid cellular automata

    NASA Astrophysics Data System (ADS)

    Mozumder, Chandan K.

    The objective in crashworthiness design is to generate plastically deformable energy absorbing structures which can satisfy the prescribed force-displacement (FD) response. The FD behavior determines the reaction force, displacement and the internal energy that the structure should withstand. However, attempts to include this requirement in structural optimization problems remain scarce. The existing commercial optimization tools utilize models under static loading conditions because of the complexities associated with dynamic/impact loading. Due to the complexity of a crash event and the consequent time required to numerically analyze the dynamic response of the structure, classical methods (i.e., gradient-based and direct) are not well developed to solve this undertaking. This work presents an approach under the framework of the hybrid cellular automaton (HCA) method to solve the above challenge. The HCA method has been successfully applied to nonlinear transient topology optimization for crashworthiness design. In this work, the HCA algorithm has been utilized to develop an efficient methodology for synthesizing shell-based sheet metal structures with optimal material thickness distribution under a dynamic loading event using topometry optimization. This method utilizes the cellular automata (CA) computing paradigm and nonlinear transient finite element analysis (FEA) via ls-dyna. In this method, a set field variables is driven to their target states by changing a convenient set of design variables (e.g., thickness). These rules operate locally in cells within a lattice that only know local conditions. The field variables associated with the cells are driven to a setpoint to obtain the desired structure. This methodology is used to design for structures with controlled energy absorption with specified buckling zones. The peak reaction force and the maximum displacement are also constrained to meet the desired safety level according to passenger safety

  9. Ultrafast photophysics of transition metal complexes.

    PubMed

    Chergui, Majed

    2015-03-17

    The properties of transition metal complexes are interesting not only for their potential applications in solar energy conversion, OLEDs, molecular electronics, biology, photochemistry, etc. but also for their fascinating photophysical properties that call for a rethinking of fundamental concepts. With the advent of ultrafast spectroscopy over 25 years ago and, more particularly, with improvements in the past 10-15 years, a new area of study was opened that has led to insightful observations of the intramolecular relaxation processes such as internal conversion (IC), intersystem crossing (ISC), and intramolecular vibrational redistribution (IVR). Indeed, ultrafast optical spectroscopic tools, such as fluorescence up-conversion, show that in many cases, intramolecular relaxation processes can be extremely fast and even shorter than time scales of vibrations. In addition, more and more examples are appearing showing that ultrafast ISC rates do not scale with the magnitude of the metal spin-orbit coupling constant, that is, that there is no heavy-atom effect on ultrafast time scales. It appears that the structural dynamics of the system and the density of states play a crucial role therein. While optical spectroscopy delivers an insightful picture of electronic relaxation processes involving valence orbitals, the photophysics of metal complexes involves excitations that may be centered on the metal (called metal-centered or MC) or the ligand (called ligand-centered or LC) or involve a transition from one to the other or vice versa (called MLCT or LMCT). These excitations call for an element-specific probe of the photophysics, which is achieved by X-ray absorption spectroscopy. In this case, transitions from core orbitals to valence orbitals or higher allow probing the electronic structure changes induced by the optical excitation of the valence orbitals, while also delivering information about the geometrical rearrangement of the neighbor atoms around the atom of

  10. 40 CFR 721.4596 - Diazo substituted carbomonocyclic metal complex.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... metal complex. 721.4596 Section 721.4596 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4596 Diazo substituted carbomonocyclic metal complex. (a) Chemical... as a diazo substituted carbomonocyclic metal complex (PMN P-94-1039) is subject to reporting...

  11. 40 CFR 721.4596 - Diazo substituted carbomonocyclic metal complex.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... metal complex. 721.4596 Section 721.4596 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4596 Diazo substituted carbomonocyclic metal complex. (a) Chemical... as a diazo substituted carbomonocyclic metal complex (PMN P-94-1039) is subject to reporting...

  12. 40 CFR 721.10104 - Halophosphate mixed metal complex (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Halophosphate mixed metal complex... Specific Chemical Substances § 721.10104 Halophosphate mixed metal complex (generic). (a) Chemical... as halophosphate mixed metal complex (PMN P-04-254) is subject to reporting under this section...

  13. 40 CFR 721.4596 - Diazo substituted carbomonocyclic metal complex.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... metal complex. 721.4596 Section 721.4596 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4596 Diazo substituted carbomonocyclic metal complex. (a) Chemical... as a diazo substituted carbomonocyclic metal complex (PMN P-94-1039) is subject to reporting...

  14. 40 CFR 721.10104 - Halophosphate mixed metal complex (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Halophosphate mixed metal complex... Specific Chemical Substances § 721.10104 Halophosphate mixed metal complex (generic). (a) Chemical... as halophosphate mixed metal complex (PMN P-04-254) is subject to reporting under this section...

  15. 40 CFR 721.10104 - Halophosphate mixed metal complex (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Halophosphate mixed metal complex... Specific Chemical Substances § 721.10104 Halophosphate mixed metal complex (generic). (a) Chemical... as halophosphate mixed metal complex (PMN P-04-254) is subject to reporting under this section...

  16. 40 CFR 721.10104 - Halophosphate mixed metal complex (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Halophosphate mixed metal complex... Specific Chemical Substances § 721.10104 Halophosphate mixed metal complex (generic). (a) Chemical... as halophosphate mixed metal complex (PMN P-04-254) is subject to reporting under this section...

  17. 40 CFR 721.10104 - Halophosphate mixed metal complex (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halophosphate mixed metal complex... Specific Chemical Substances § 721.10104 Halophosphate mixed metal complex (generic). (a) Chemical... as halophosphate mixed metal complex (PMN P-04-254) is subject to reporting under this section...

  18. 40 CFR 721.4596 - Diazo substituted carbomonocyclic metal complex.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... metal complex. 721.4596 Section 721.4596 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4596 Diazo substituted carbomonocyclic metal complex. (a) Chemical... as a diazo substituted carbomonocyclic metal complex (PMN P-94-1039) is subject to reporting...

  19. 40 CFR 721.4596 - Diazo substituted carbomonocyclic metal complex.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... metal complex. 721.4596 Section 721.4596 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4596 Diazo substituted carbomonocyclic metal complex. (a) Chemical... as a diazo substituted carbomonocyclic metal complex (PMN P-94-1039) is subject to reporting...

  20. Asbestos disease in sheet metal workers: the results of a proportional mortality analysis

    SciTech Connect

    Zoloth, S.; Michaels, D.

    1985-01-01

    The results of a proportional mortality analysis of a cohort of sheet metal workers who have only intermittent exposure to asbestos demonstrates a significant excess of cancer at the three sites most frequently associated with asbestos: lung, colon and rectum, and the mesothelium. No excess nonmalignant respiratory disease was detected. These data strongly suggest that significant asbestos-related disease is present in populations with secondary exposure to asbestos and emphasize the importance of considering possible asbestos-related disease when treating patients with a history of employment in the construction industry.

  1. Implementation Of The Artificial Neural Networks To Control The Springback Of Metal Sheets

    NASA Astrophysics Data System (ADS)

    Crina, Axinte

    2007-05-01

    Geometrical inaccuracy of sheet metal parts due to the springback phenomenon is the reason for considerable efforts in tools and process development. Prediction of springback is a key issue to design the tools and control the process parameters in order to obtain close tolerances in the formed parts. The objective of this paper is to use simulation procedure coupled with neural networks method to get the best relation between process parameters and tools geometry in order to minimize the shape deviations of the formed parts related to the target geometry.

  2. Numerical Analysis of the Resistance to Shear Test of Clinched Assemblies of Thin Metal Sheets

    SciTech Connect

    Jomaa, Moez; Billardon, Rene

    2007-05-17

    The work presented in this paper is part of a more extensive study the aim of which is to build a complete simulation of the clinching process and subsequent resistance tests. This paper focuses on finite element analyses - that are performed with the ABAQUS code - of the resistance of clinched points to shear test. These analyses are run up to propagation of metal sheet fracture. A simplified procedure is proposed to identify the fracture initiation and propagation models that are used to simulate this failure process. This identification process is based on Lemaitre's ductile damage model. The numerical simulations of a shear test have been compared to experimental results.

  3. Control the springback of metal sheets by using an artificial neural network

    SciTech Connect

    Crina, Axinte

    2007-04-07

    One of the greatest challenges of manufacturing sheet metal parts is to obtain consistent parts dimensions. Springback is the major cause of variations and inconsistencies in the final part geometry. Obtaining a consistent and desirable amount of springback is extremely difficult due to the non-linear effects and interactions of process and material parameters. In this work, the ability of an artificial neural network model to predict optimum process parameters and tools geometry which allow to obtain minimum amount of springback is tested, in the case of a cylindrical deep-drawing process.

  4. Implementation Of The Artificial Neural Networks To Control The Springback Of Metal Sheets

    SciTech Connect

    Crina, Axinte

    2007-05-17

    Geometrical inaccuracy of sheet metal parts due to the springback phenomenon is the reason for considerable efforts in tools and process development. Prediction of springback is a key issue to design the tools and control the process parameters in order to obtain close tolerances in the formed parts. The objective of this paper is to use simulation procedure coupled with neural networks method to get the best relation between process parameters and tools geometry in order to minimize the shape deviations of the formed parts related to the target geometry.

  5. Aircraft Metal Skin Repair and Honeycomb Structure Repair; Sheet Metal Work 3: 9857.02.

    ERIC Educational Resources Information Center

    Dade County Public Schools, Miami, FL.

    The course helps students determine types of repairs, compute repair sizes, and complete the repair through surface protection. Course content includes goals, specific objectives, protection of metals, repairs to metal skin, and honeycomb structure repair. A bibliography and post-test are appended. A prerequisite for this course is mastery of the…

  6. Analysis of metal-EDTA complexes by electrospray mass spectrometry

    SciTech Connect

    Baron, D.; Hering, J.G.

    1998-07-01

    Solutions of the strong complexing agent ethylenediaminetetraacetic acid (EDTA) and Cu, Pb, Cd, Al, and Fe(III) were examined by electrospray mass spectrometry (ES/MS). Uncomplexed EDTA and metal-EDTA complexes survive the electrospray process intact and can be detected simultaneously by mass spectrometry. Best sensitivity was achieved in the positive ion mode in which EDTA and EDTA-metal complexes (present in solution as anions) were detected as protonated species with a single positive charge. Except for the protonation, the aqueous metal-EDTA complexes are preserved and neither fragmentation of complexes nor formation of clusters with more than one metal or ligand were observed in the mass spectra. Detection limits are between approximately 1 to 2 {micro}M for uncomplexed EDTA and for the Cu-EDTA and Pb-EDTA complexes, with a linear range up to 10{sup {minus}4} M. Calibrations based on solutions with equimolar concentrations of EDTA and Cu or Pb can be used to quantify EDTA-metal complexes in solutions with excess EDTA or metal, and in solutions with more than one metal present. Isotopic signatures of metals in the metal-ligand complexes are preserved, allowing the identification of the metal in a metal-ligand complex. Isotopic signatures of metals can therefore aid in the identification of metal-ligand complexes in unknown samples.

  7. Mutual Inductance Problem for a System Consisting of a Current Sheet and a Thin Metal Plate

    NASA Technical Reports Server (NTRS)

    Fulton, J. P.; Wincheski, B.; Nath, S.; Namkung, M.

    1993-01-01

    Rapid inspection of aircraft structures for flaws is of vital importance to the commercial and defense aircraft industry. In particular, inspecting thin aluminum structures for flaws is the focus of a large scale R&D effort in the nondestructive evaluation (NDE) community. Traditional eddy current methods used today are effective, but require long inspection times. New electromagnetic techniques which monitor the normal component of the magnetic field above a sample due to a sheet of current as the excitation, seem to be promising. This paper is an attempt to understand and analyze the magnetic field distribution due to a current sheet above an aluminum test sample. A simple theoretical model, coupled with a two dimensional finite element model (FEM) and experimental data will be presented in the next few sections. A current sheet above a conducting sample generates eddy currents in the material, while a sensor above the current sheet or in between the two plates monitors the normal component of the magnetic field. A rivet or a surface flaw near a rivet in an aircraft aluminum skin will disturb the magnetic field, which is imaged by the sensor. Initial results showed a strong dependence of the flaw induced normal magnetic field strength on the thickness and conductivity of the current-sheet that could not be accounted for by skin depth attenuation alone. It was believed that the eddy current imaging method explained the dependence of the thickness and conductivity of the flaw induced normal magnetic field. Further investigation, suggested the complexity associated with the mutual inductance of the system needed to be studied. The next section gives an analytical model to better understand the phenomenon.

  8. Towards comprehensive cell lineage reconstructions in complex organisms using light-sheet microscopy.

    PubMed

    Amat, Fernando; Keller, Philipp J

    2013-05-01

    Understanding the development of complex multicellular organisms as a function of the underlying cell behavior is one of the most fundamental goals of developmental biology. The ability to quantitatively follow cell dynamics in entire developing embryos is an indispensable step towards such a system-level understanding. In recent years, light-sheet fluorescence microscopy has emerged as a particularly promising strategy for recording the in vivo data required to realize this goal. Using light-sheet fluorescence microscopy, entire complex organisms can be rapidly imaged in three dimensions at sub-cellular resolution, achieving high temporal sampling and excellent signal-to-noise ratio without damaging the living specimen or bleaching fluorescent markers. The resulting datasets allow following individual cells in vertebrate and higher invertebrate embryos over up to several days of development. However, the complexity and size of these multi-terabyte recordings typically preclude comprehensive manual analyses. Thus, new computational approaches are required to automatically segment cell morphologies, accurately track cell identities and systematically analyze cell behavior throughout embryonic development. We review current efforts in light-sheet microscopy and bioimage informatics towards this goal, and argue that comprehensive cell lineage reconstructions are finally within reach for many key model organisms, including fruit fly, zebrafish and mouse.

  9. Analysis of hot forming of a sheet metal component made of advanced high strength steel

    NASA Astrophysics Data System (ADS)

    Demirkaya, Sinem; Darendeliler, Haluk; Gökler, Mustafa İlhan; Ayhaner, Murat

    2013-05-01

    To provide reduction in weight while maintaining crashworthiness and to decrease the fuel consumption of vehicles, thinner components made of Advanced High Strength Steels (AHSS) are being increasingly used in automotive industry. However, AHSS cannot be formed easily at the room temperature (i.e. cold forming). The alternative process involves heating, hot forming and subsequent quenching. A-pillar upper reinforcement of a vehicle is currently being produced by cold forming of DP600 steel sheet with a thickness of 1.8 mm. In this study, the possible decrease in the thickness of this particular part by using 22MnB5 as appropriate AHSS material and applying this alternative process has been studied. The proposed process involves deep drawing, trimming, heating, sizing, cooling and piercing operations. Both the current production process and the proposed process are analyzed by the finite element method. The die geometry, blank holding forces and the design of the cooling channels for the cooling process are determined numerically. It is shown that the particular part made of 22MnB5 steel sheet with a thickness of 1.2 mm can be successfully produced by applying the proposed process sequence and can be used without sacrificing the crashworthiness. With the use of the 22MnB5 steel with a thickness of 1.2 mm instead of DP600 sheet metal with a thickness of 1.8 mm, the weight is reduced by approximately 33%.

  10. An exact derivation of contact resistance to planar devices. [metal surface on semiconductor sheet

    NASA Technical Reports Server (NTRS)

    Schuldt, S. B.

    1978-01-01

    A mixed boundary-value problem is formulated for an imperfect rectangular contact to a semiconducting sheet (layer). An exact model for derivation of contact resistance is developed and its solution by conformal mapping and eigenfunction expansion is presented. The expression for contact resistance is similar to that for a perfect (lossless) contact but includes an additional term containing the lowest-order coefficient in the infinite series expansion of the complex potential function. The calculated contact resistances are compared with those obtained from three approximate models: lossless contact, transmission line, and extended transmission line models. The extended transmission line model appears to be a very satisfactory approximation provided the ratio of contact length to sheet thickness is no less than 0.5.

  11. Transition Metal Complexes of Expanded Porphyrins

    PubMed Central

    Sessler, Jonathan L.; Tomat, Elisa

    2008-01-01

    Over the last two decades, the rapid development of new synthetic routes for the preparation of expanded porphyrin macrocycles has allowed exploration of a new frontier consisting of “porphyrin-like” coordination chemistry. In this Account, we summarize our exploratory forays into the still relatively poorly explored area of oligopyrrolic macrocycle metalation chemistry. Specifically, we describe our successful formation of both mono- and binuclear complexes and in doing so highlight the diversity of coordination modes available to expanded porphyrin-type ligands. The nature of the inserted cation, the emerging role of tautomeric equilibria, and the importance of hydrogen-bonding interactions in regulating this chemistry are also discussed. PMID:17397134

  12. Simulation and measurement of melting effects on metal sheets caused by direct lightning strikes

    NASA Technical Reports Server (NTRS)

    Kern, Alexander

    1991-01-01

    Direct lightning strikes melt metal parts of various systems, like fuel and propellant tanks of rockets and airplanes, at the point of strike. Responsible for this melting are the impulse current and, if occurring, the long duration current, both carrying a remarkable charge Q. For studying these meltings the simulation in the laboratory has to be based on the parameters of natural lightnings. International standards exist defining certain threat levels of natural lightnings and giving possible generator circuits for the simulation. The melting caused by both types of lightning currents show different appearance. Their characteristics, their differences in melting and heating of metal sheets are investigated. Nevertheless the simulation of lightning in the laboratory is imperfect. While natural lightning is a discharge without a counter electrode, the simulation always demands a close counter electrode. The influence of this counter electrode is studied.

  13. Peptide binding to sheet silicate and metal nanoparticles: Insight from atomistic simulation

    NASA Astrophysics Data System (ADS)

    Heinz, Hendrik; Pandey, Ras B.; Drummy, Lawrence; Vaia, Richard A.; Naik, Rajesh R.; Farmer, Barry L.

    2008-03-01

    Short peptides (8 to 12 amino acids, excluding Cys) bind selectively to nanoparticles composed of Au, Pd, and montmorillonite depending on the sequence of amino acids, as evidenced by laboratory screening of several billion peptides. The molecular reasons for binding versus non-binding and the specificity toward a certain surface are analyzed by molecular dynamics simulation, using recent force field extensions for fcc metals and sheet silicates to reproduce surface and interface energies with <10% deviation compared to experiment. Polarization on even metal surfaces ranges from 3 to 5 kcal/mol and non-covalent binding energies from 0 and 80 kcal/mol per dodecapeptide. Adsorption energies, changes in chain conformation, Ramachandran plots, and orientational parameters, are analyzed in conjunction with NMR, TEM, and other experimental data. On montmorillonite, an ion exchange reaction of Lys side groups against alkali ions as well as interactions between alkali cations and polar groups in the peptide are explained.

  14. Evidencing the existence of exciting half-metallicity in two-dimensional TiCl3 and VCl3 sheets

    NASA Astrophysics Data System (ADS)

    Zhou, Yungang; Lu, Haifeng; Zu, Xiaotao; Gao, Fei

    2016-01-01

    Half-metallicity combined with wide half-metallic gap, unique ferromagnetic character and high Curie temperature has become a key driving force to develop next-generation spintronic devices. In previous studies, such half-metallicity always occurred under certain manipulation. Here, we, via examining a series of two-dimensional transition-metal trichlorides, evidenced that TiCl3 and VCl3 sheets could display exciting half-metallicity without involving any external modification. Calculated half-metallic band-gaps for TiCl3 and VCl3 sheets are about 0.60 and 1.10 eV, respectively. Magnetic coupled calculation shows that both sheets favor the ferromagnetic order with a substantial collective character. Estimated Curie temperatures can be up to 376 and 425 K for TiCl3 and VCl3 sheets, respectively. All of these results successfully disclose two new promising two-dimensional half-metallic materials toward the application of next-generation paper-like spintronic devices.

  15. Evidencing the existence of exciting half-metallicity in two-dimensional TiCl3 and VCl3 sheets

    PubMed Central

    Zhou, Yungang; Lu, Haifeng; Zu, Xiaotao; Gao, Fei

    2016-01-01

    Half-metallicity combined with wide half-metallic gap, unique ferromagnetic character and high Curie temperature has become a key driving force to develop next-generation spintronic devices. In previous studies, such half-metallicity always occurred under certain manipulation. Here, we, via examining a series of two-dimensional transition-metal trichlorides, evidenced that TiCl3 and VCl3 sheets could display exciting half-metallicity without involving any external modification. Calculated half-metallic band-gaps for TiCl3 and VCl3 sheets are about 0.60 and 1.10 eV, respectively. Magnetic coupled calculation shows that both sheets favor the ferromagnetic order with a substantial collective character. Estimated Curie temperatures can be up to 376 and 425 K for TiCl3 and VCl3 sheets, respectively. All of these results successfully disclose two new promising two-dimensional half-metallic materials toward the application of next-generation paper-like spintronic devices. PMID:26776358

  16. Cruciform specimen design and validation for constitutive identification of sheet metal

    NASA Astrophysics Data System (ADS)

    Deng, Nengxiu; Korkolis, Yannis P.

    2013-12-01

    Accurate material models are imperative for successful simulations of sheet metal forming. Calibrating these models can benefit significantly from biaxial experimental data, for example by testing cruciform specimens under biaxial tension. While this technique allows for significant flexibility in the strain paths that can be investigated, a major limitation is the difficulty of accurately determining the stresses in the test section. We propose a cruciform specimen design that allows for direct and accurate determination of stresses from remote load and local strain measurements. The specimen has a test section of reduced thickness; sharp radii and step transitions between the arms and the test section; and laser-cut slots in the four arms. Using finite element analysis, we show that these features result in a uniform stress field inside the test section, with the exception of a thin boundary layer between the arms and the test section. Furthermore, we show numerically that this specimen design can very accurately recover the hardening behavior and the yield surface of the material for strains exceeding 15% for a dual-phase steel (DP590), depending on the loading path. While very accurate for constitutive identification, this design cannot be used to assess the forming limits of sheet metal as failure initiates at the thin boundary layer at the periphery of the test section.

  17. Method of manufacturing metallic products such as sheet by cold working and flash annealing

    DOEpatents

    Hajaligol, Mohammad R.; Sikka, Vinod K.

    2000-01-01

    A metallic alloy composition is manufactured into products such as press formed or stamped products or rolled products such as sheet, strip, rod, wire or band by one or more cold working steps with intermediate or final flash annealing. The method can include cold rolling an iron, nickel or titanium aluminide alloy and annealing the cold worked product in a furnace by infrared heating. The flash annealing is preferably carried out by rapidly heating the cold worked product to an elevated temperature for less than one minute. The flash annealing is effective to reduce surface hardness of the cold worked product sufficiently to allow further cold working. The product to be cold worked can be prepared by casting the alloy or by a powder metallurgical technique such as tape casting a mixture of metal powder and a binder, roll compacting a mixture of the powder and a binder or plasma spraying the powder onto a substrate. In the case of tape casting or roll compaction, the initial powder product can be heated to a temperature sufficient to remove volatile components. The method can be used to form a cold rolled sheet which is formed into an electrical resistance heating element capable of heating to 900.degree. C. in less than 1 second when a voltage up to 10 volts and up to 6 amps is passed through the heating element.

  18. Method of manufacturing metallic products such as sheet by cold working and flash anealing

    DOEpatents

    Hajaligol, Mohammad R.; Sikka, Vinod K.

    2001-01-01

    A metallic alloy composition is manufactured into products such as press formed or stamped products or rolled products such as sheet, strip, rod, wire or band by one or more cold working steps with intermediate or final flash annealing. The method can include cold rolling an iron, nickel or titanium aluminide alloy and annealing the cold worked product in a furnace by infrared heating. The flash annealing is preferably carried out by rapidly heating the cold worked product to an elevated temperature for less than one minute. The flash annealing is effective to reduce surface hardness of the cold worked product sufficiently to allow further cold working. The product to be cold worked can be prepared by casting the alloy or by a powder metallurgical technique such as tape casting a mixture of metal powder and a binder, roll compacting a mixture of the powder and a binder or plasma spraying the powder onto a substrate. In the case of tape casting or roll compaction, the initial powder product can be heated to a temperature sufficient to remove volatile components. The method can be used to form a cold rolled sheet which is formed into an electrical resistance heating element capable of heating to 900.degree. C. in less than 1 second when a voltage up to 10 volts and up to 6 amps is passed through the heating element.

  19. Tunable color parallel tandem organic light emitting devices with carbon nanotube and metallic sheet interlayers

    SciTech Connect

    Oliva, Jorge; Desirena, Haggeo; De la Rosa, Elder; Papadimitratos, Alexios; Zakhidov, Anvar A.

    2015-11-21

    Parallel tandem organic light emitting devices (OLEDs) were fabricated with transparent multiwall carbon nanotube sheets (MWCNT) and thin metal films (Al, Ag) as interlayers. In parallel monolithic tandem architecture, the MWCNT (or metallic films) interlayers are an active electrode which injects similar charges into subunits. In the case of parallel tandems with common anode (C.A.) of this study, holes are injected into top and bottom subunits from the common interlayer electrode; whereas in the configuration of common cathode (C.C.), electrons are injected into the top and bottom subunits. Both subunits of the tandem can thus be monolithically connected functionally in an active structure in which each subunit can be electrically addressed separately. Our tandem OLEDs have a polymer as emitter in the bottom subunit and a small molecule emitter in the top subunit. We also compared the performance of the parallel tandem with that of in series and the additional advantages of the parallel architecture over the in-series were: tunable chromaticity, lower voltage operation, and higher brightness. Finally, we demonstrate that processing of the MWCNT sheets as a common anode in parallel tandems is an easy and low cost process, since their integration as electrodes in OLEDs is achieved by simple dry lamination process.

  20. Adaptive scallop height tool path generation for robot-based incremental sheet metal forming

    NASA Astrophysics Data System (ADS)

    Seim, Patrick; Möllensiep, Dennis; Störkle, Denis Daniel; Thyssen, Lars; Kuhlenkötter, Bernd

    2016-10-01

    Incremental sheet metal forming is an emerging process for the production of individualized products or prototypes in low batch sizes and with short times to market. In these processes, the desired shape is produced by the incremental inward motion of the workpiece-independent forming tool in depth direction and its movement along the contour in lateral direction. Based on this shape production, the tool path generation is a key factor on e.g. the resulting geometric accuracy, the resulting surface quality, and the working time. This paper presents an innovative tool path generation based on a commercial milling CAM package considering the surface quality and working time. This approach offers the ability to define a specific scallop height as an indicator of the surface quality for specific faces of a component. Moreover, it decreases the required working time for the production of the entire component compared to the use of a commercial software package without this adaptive approach. Different forming experiments have been performed to verify the newly developed tool path generation. Mainly, this approach serves to solve the existing conflict of combining the working time and the surface quality within the process of incremental sheet metal forming.

  1. Koolau dike complex, Oahu: intensity and origin of a sheeted-dike complex high in a Hawaiian volcanic edifice

    SciTech Connect

    Walker, G.P.L.

    1986-04-01

    The dike complex in the eroded Koolau tholeiitic shield volcano is unique among described dike swarms for its coherence, high dike-injection intensity, relatively uniform and non-Gaussian 50% to 65% intensity level, and lack of dike divergence. Parts are like a sheeted-dike complex, though high in an intraplate volcanic edifice. A model is proposed in which highly mobile tholeiitic magma, having considerable freedom to move through the strongly disjointed volcano, seeks zones in which it is gravitationally most stable. These zones are marginal parts of the dike complex, separating lavas having a lower-than-magmatic bulk density from a > 50% dike complex having a higher-than-magmatic bulk density. This model also explains the strong propensity for the magma of Kilauea volcano to remain underground (in a gravitationally stable zone). Magma erupts only when it vesiculates sufficiently; often, when it has degassed, some of it promptly plunges back toward the stable zone again.

  2. Implementation of virtual models from sheet metal forming simulation into physical 3D colour models using 3D printing

    NASA Astrophysics Data System (ADS)

    Junk, S.

    2016-08-01

    Today the methods of numerical simulation of sheet metal forming offer a great diversity of possibilities for optimization in product development and in process design. However, the results from simulation are only available as virtual models. Because there are any forming tools available during the early stages of product development, physical models that could serve to represent the virtual results are therefore lacking. Physical 3D-models can be created using 3D-printing and serve as an illustration and present a better understanding of the simulation results. In this way, the results from the simulation can be made more “comprehensible” within a development team. This paper presents the possibilities of 3D-colour printing with particular consideration of the requirements regarding the implementation of sheet metal forming simulation. Using concrete examples of sheet metal forming, the manufacturing of 3D colour models will be expounded upon on the basis of simulation results.

  3. Explosive Welding of Aluminum, Titanium and Zirconium to Copper Sheet Metal

    NASA Technical Reports Server (NTRS)

    Hegazy, A. A.; Mote, J. D.

    1985-01-01

    The main material properties affecting the explosive weldability of a certain metal combination are the yield strength, the ductility, the density and the sonic velocity of the two metals. Successful welding of the metal combination depends mainly on the correct choice of the explosive welding parameters; i.e., the stand off distance, the weight of the explosive charge relative to the weight of the flyer plate and the detonation velocity of the explosive. Based on the measured and the handbook values of the properties of interest, the explosive welding parameters were calculated and the arrangements for the explosive welding of the Al alloy 6061-T6, titanium and zirconium to OFHC copper were determined. The relatively small sheet metal thickness (1/8") and the fact that the thickness of the explosive layer must exceed a certain minimum value were considered during the determination of the explosive welding conditions. The results of the metallographic investigations and the measurements of the shear strength at the interface demonstrate the usefulness of these calculations to minimize the number of experimental trials.

  4. Metal encapsulating carbon nanostructures from oligoalkyne metal complexes

    SciTech Connect

    Dosa, P.I.; Erben, C.; Iyer, V.S.; Vollhardt, K.P.C.; Wasser, I.M.

    1999-11-10

    Carbon nanotubes, onions, and related closed-shell carbon particles have commanded extensive recent attention because of their potential applications as unique electronic, magnetic, and mechanically robust materials. When filled with metals, such nanocapsules have additional promise as magnetic particles, contrasting agents, protecting cloaks, and catalysts and in other applications. Among the various methods for their preparation, the transition metal (especially Fe, Co, and Ni) catalyzed pyrolysis of small organic molecules has shown promise for larger scale production and in structural control. While the use of organometallic complexes as solid catalyst precursors or copyrolytic gaseous ingredients has been reported, all of these studies have been limited to gas-phase experiments at relatively high temperatures. There is very little literature that deals with the organic solid-state generation of carbon nanotubes. The latter suffers from extreme conditions, poor yields, or not readily modifiable starting materials. Development of synthetic organic approaches to closed shell large carbon structures is desirable but in its infancy. Here the authors present a significant step in its progress.

  5. 40 CFR 721.4594 - Substituted azo metal complex dye.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Substituted azo metal complex dye. 721... Substances § 721.4594 Substituted azo metal complex dye. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a substituted azo metal...

  6. 40 CFR 721.4594 - Substituted azo metal complex dye.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Substituted azo metal complex dye. 721... Substances § 721.4594 Substituted azo metal complex dye. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a substituted azo metal...

  7. 40 CFR 721.4594 - Substituted azo metal complex dye.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Substituted azo metal complex dye. 721... Substances § 721.4594 Substituted azo metal complex dye. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a substituted azo metal...

  8. 40 CFR 721.4594 - Substituted azo metal complex dye.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Substituted azo metal complex dye. 721... Substances § 721.4594 Substituted azo metal complex dye. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a substituted azo metal...

  9. 40 CFR 721.4594 - Substituted azo metal complex dye.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted azo metal complex dye. 721... Substances § 721.4594 Substituted azo metal complex dye. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a substituted azo metal...

  10. Waste minimization assessment for a manufacturer of iron castings and fabricated sheet metal parts

    SciTech Connect

    Fleischman, M.; Harris, J.J.; Handmaker, A.; Looby, G.P.

    1995-08-01

    The U.S. Environmental Protection Agency (EPA) has funded a pilot project to assist small and medium-size manufacturers who want to minimize their generation of waste but who lack the expertise to do so. Waste Minimization Assessment Centers (WMACs) were established at selected universities and procedures were adapted from the EPA Waste Minimization Opportunity Assessment Manual. That document has been superseded by the Facility Pollution Prevention Guide. The WMAC team at the University of Louisville performed an assessment at a plant that manufactures iron castings and fabricated sheet metal parts. Foundry operations include mixing and mold formation, core making, metal pouring, shakeout, finishing, and painting. Cutting, shaping, and welding are the principal metal fabrication operations. The team`s report, detailing findings and recommendations indicated that paint-related wastes are generated in large quantities, and that significant waste reduction and cost savings could be realized by installing a dry powder coating system or by replacing conventional air spray paint guns with high-volume low-pressure spray guns. This research brief was developed by the principal investigators and EPA`s National Risk Management Research Laboratory, Cincinnati, OH, to announce key findings of an ongoing research project that is fully documented in a separate report of the same title available from University City Science Center.

  11. Numerical Determination of Sheet Metal Formability under Simultaneous Stretching and Bending

    NASA Astrophysics Data System (ADS)

    Martinezhyphen; Lopez, A.; van den Boogaard, A. H.

    2011-01-01

    The plastic behavior of AHSS is still far from being completely understood, and its prediction is of large importance in reliability of forming simulation in present automotive industry [1]. Conventional techniques have been proven to be not accurate enough, and underestimate the formability limits for AHSS materials in cases where stretching and bending are combined. In order to satisfy industrial requirements more work need to be done to understand the formability behavior of sheet metal, and special attention needs to be directed to the possible reasons of the lower predicted formability limits. In previous work [2], experimental results for different materials confirmed the positive effect of bending in terms of formability, and demonstrated the influence of curvature on the FLC is especially clear in the plane strain region. Using conventionally determined FLC could lead to not optimal material consumption during sheet forming operations. For this reason, in this study 3D Finite Element simulations were developed using the commercial code ABAQUS/Standard to investigate further the effect of the out of plane stress, and punch radii for the FLC determination. Also the investigation of the influence of different lubrication systems was accomplished.

  12. Sheet metal welding using a pulsed Nd: YAG laser-robot

    NASA Astrophysics Data System (ADS)

    Huang, Qi; Kullberg, Gunnar; Skoog, Hans

    This paper presents a pulsed Nd: YAG laser-robot system for spot and seam welding of mild steel sheets. The study evaluates the laser beams behaviour for welding, and then investigates pulsed Nd: YAG laser spot and seam welding processes. High pulse power intensity is needed to initiate the key-hole welding process and a threshold pulse energy to reach full penetration. In seam welding, a weld consists of successive overlapping spots. Both high pulse energy and high average power are needed to keep the key-hole welding going. A 70% overlap is used to define overlapping spot welding as seam welding and to optimize process parameters because a high tensile strength joint compatible with the strength of the base material can be obtained when the overlap is ≥ 70%; at the same time a smooth seam with full penetration is obtained. In these cases, the joints in pulsed Nd: YAG laser welding are comparable in strength to those obtained with CO 2 laser welding. Robot positioning and motion accuracies can meet the demands of Nd: YAG laser sheet metal welding, but its cornering accuracy affects the welding processes. The purpose of the study is to evaluate the YAG laser-robot system for production in the automotive industry.

  13. Tool path influence on electric pulse aided deformation during incremental sheet metal forming

    SciTech Connect

    Asgar, J.; Lingam, R. Reddy, V. N.

    2013-12-16

    Titanium and its alloys are difficult to form at room temperature due to their high flow stress. Super plastic deformation of Ti alloys involves low strain rate forming at very high temperatures which need special tooling which can withstand high temperatures. It was observed that when high current density electric pulse is applied during deformation it reduces the flow stress through electron-dislocation interaction. This phenomenon is known as electro-plasticity. In the present work, importance of tool configuration to enhance the formability without much resistive heating is demonstrated for Incremental Sheet Metal Forming (ISMF). Tool configuration is selected to minimize the current carrying zone in DC pulse aided incremental forming to enhance the formability due to electro plasticity and the same is demonstrated by forming two pyramid shaped components of 30° and 45° wall angles using a Titanium alloy sheet of 0.6 mm thickness. Load measurement indicated that a critical current density is essential for the electro-plasticity to be effective and the same is realized with the load and temperature measurements.

  14. Consistent Parameters for Plastic Anisotropy of Sheet Metal (Part 1-Uniaxial and Biaxial Tests)

    SciTech Connect

    Poehlandt, K.; Schoeck, J.; Lange, K.; Banabic, D.

    2007-04-07

    The anisotropy parameters for sheet metal used hitherto are mainly determined by uniaxial tensile tests. Such tests, however, do not give sufficient information about the yield locus and the forming behaviour in that range where the two principal tensile stresses are of similar magnitude like in stretch forming. The same applies for combined tensile and compressive stress like in deep-drawing. To fill these gaps, new parameters are defined. Their experimental determination is briefly discussed.The 'equibiaxial yield stress' and 'equibiaxial anisotropy' which refer to equibiaxial tensile stress can be determined by cross tensile tests. However, these require a special apparatus. Alternatively experiments for obtaining plane strain can be applied for determining the equibiaxial parameters indirectly. This is possible using conventional tensile testing machines. In this case also anisotropy parameters for plane-strain deformation, the 'semibiaxial anisotropy' in rolling and transverse direction, can be determined.

  15. Friction and lubrication modelling in sheet metal forming simulations of the Volvo XC90 inner door

    NASA Astrophysics Data System (ADS)

    Sigvant, M.; Pilthammar, J.; Hol, J.; Wiebenga, J. H.; Chezan, T.; Carleer, B.; van den Boogaard, A. H.

    2016-08-01

    The quality of sheet metal formed parts is strongly dependent on the friction and lubrication conditions that are acting in the actual production process. Although friction is of key importance, it is currently not considered in detail in stamping simulations. This paper presents project results considering friction and lubrication modelling in stamping simulations of the Volvo XC90 inner door. For this purpose, the TriboForm software is used in combination with the AutoForm software. Validation of the simulation results is performed based on door-inner parts taken from the press line in a full-scale production run. The project results demonstrate the improved prediction accuracy of stamping simulations.

  16. Fatigue Behaviors of Self-Piercing Rivets Joining Similar and Dissimilar Sheet Metals

    SciTech Connect

    Sun, Xin; Stephens, Elizabeth V.; Khaleel, Mohammad A.

    2007-01-01

    This paper summarizes the fatigue test results of self-piercing rivet (SPR) joints between similar and dissimilar sheet metals. The influences of material grades, material thickness, piercing direction and the use of structural adhesive on the rivet samples’ fatigue behaviors were investigated. Fatigue test results indicate that SPR joints have superior fatigue strength than resistance spot weld (RSW) joints for the same material combinations. The application of structure adhesive also significantly enhances the fatigue strength of the joint samples; this is particularly true for the lap shear loading configuration. In addition, different piercing directions for SPR joints have a noticeable effect on the static and fatigue strength of the joints. The joint fatigue results presented in this paper can offer design engineers with the durability data for SPR joints with these material combinations. Moreover, it will provide manufacturing engineers with some insights on the effects of different manufacturing parameters on the strength and durability of these joints.

  17. Energetic characteristics of transition metal complexes.

    PubMed

    Wojewódka, Andrzej; Bełzowski, Janusz; Wilk, Zenon; Staś, Justyna

    2009-11-15

    Ten transition metal nitrate and perchlorate complexes of hydrazine and ethylenediamine were synthesized, namely [Cu(EN)(2)](ClO(4))(2), [Co(EN)(3)](ClO(4))(3), [Ni(EN)(3)](ClO(4))(2), [Hg(EN)(2)](ClO(4))(2), [Cr(N(2)H(4))(3)](ClO(4))(3), [Cd(N(2)H(4))(3)](ClO(4))(2), [Ni(N(2)H(4))(3)](NO(3))(2), [Co(N(2)H(4))(3)](NO(3))(3), [Zn(N(2)H(4))(3)](NO(3))(2), and [Cd(N(2)H(4))(3)](NO(3))(2) based on the lines of the literature reported methods. All of them were tested with applying underwater detonation test and further compared to the typical blasting explosives: RDX, HMX, TNT and PETN. From the above presented complexes [Ni(N(2)H(4))(3)](NO(3))(2) (called NHN) and [Co(N(2)H(4))(3)](NO(3))(3) (called CoHN) are known as primary explosives and can be used as the standard explosives. Explosion parameters, such as shock wave overpressure, shock wave energy equivalent and bubble energy equivalent, were determined. Evaluated energetic characteristics of the tested compounds are comparable to those of the classic high explosives and are even enhanced in some cases.

  18. Complexation of Uranium by Cells and S-Layer Sheets of Bacillus sphaericus JG-A12

    PubMed Central

    Merroun, Mohamed L.; Raff, Johannes; Rossberg, André; Hennig, Christoph; Reich, Tobias; Selenska-Pobell, Sonja

    2005-01-01

    Bacillus sphaericus JG-A12 is a natural isolate recovered from a uranium mining waste pile near the town of Johanngeorgenstadt in Saxony, Germany. The cells of this strain are enveloped by a highly ordered crystalline proteinaceous surface layer (S-layer) possessing an ability to bind uranium and other heavy metals. Purified and recrystallized S-layer proteins were shown to be phosphorylated by phosphoprotein-specific staining, inductive coupled plasma mass spectrometry analysis, and a colorimetric method. We used extended X-ray absorption fine-structure (EXAFS) spectroscopy to determine the structural parameters of the uranium complexes formed by purified and recrystallized S-layer sheets of B. sphaericus JG-A12. In addition, we investigated the complexation of uranium by the vegetative bacterial cells. The EXAFS analysis demonstrated that in all samples studied, the U(VI) is coordinated to carboxyl groups in a bidentate fashion with an average distance between the U atom and the C atom of 2.88 ± 0.02 Å and to phosphate groups in a monodentate fashion with an average distance between the U atom and the P atom of 3.62 ± 0.02 Å. Transmission electron microscopy showed that the uranium accumulated by the cells of this strain is located in dense deposits at the cell surface. PMID:16151146

  19. Early Transition Metal Alkyl and Tetrahydroborate Complexes.

    NASA Astrophysics Data System (ADS)

    Jensen, James Allen

    1988-06-01

    An investigation of early transition metal alkyl and tetrahydroborate complexes as catalytic models and ceramic precursors has been initiated. The compounds MX _2 (dmpe)_2, dmpe = 1,2-bis(dimethylphosphino)ethane, for M = Ti, V, Cr, and X = Br, I, BH_4, have been prepared. These complexes are paramagnetic and have been shown by X-ray crystallography to have trans-octahedral structures. The BH_4^{-} groups in Ti(BH_4)_2(dmpe) _2 bond to the metal in a bidentate manner. This structure is in marked contrast to the structure of the vanadium analogue, V(BH_4)_2 (dmpe)_2, which displays two unidentate BH_4^{-} groups. Alkylation of Ti(BH_4)_2 (dmpe)_2 with LiMe results in the complex TiMe_2(dmpe) _2 which is diamagnetic in both solution and solid state. Single crystal X-ray and neutron diffraction studies show that there may be strong Ti-C pi -bonding. A tetragonal compression along the C -Ti-C bond vector accounts for the observed diamegnetism. A series of complexes of the formula Ti(BH _4)_3(PR_3)_2 has been prepared where PR_3 = PMe_3, PEt_3, PMe_3Ph, and P(OMe)_3 . The X-ray crystal structure of Ti(BH _4)_3(PMe_3)_2 reveals a pseudo trigonal bipyramidal geometry in which two BH_4^{-} groups display an unusual "side-on" bonding mode. The "side-on" ligation mode has been attributed to a Jahn-Teller distortion of the orbitally degenerate d^1 ground state. In contrast, the non-Jahn-Teller susceptible vanadium analogue, V(BH_4)_3 (PMe_3)_2, possesses a nearly ideal D_{rm 3h} >=ometry with three bidentate tetrahydroborate groups. Addition of excess PMe_3 to V(BH_4)_3(PMe _3)_2<=ads to the vanadium(II) hydride -bridged dimer (V(H)(BH_4)(PMe _3)_2]_2, while addition of PMe_3 and water forms the vanadium(III) oxo dimer (V(BH_4)_2 (PMe_3)_2]_2 [mu-O) which has been structurally characterized. The compound Ti(CH_2CMe _3)_4 can be prepared by addition of Ti(OEt)_4 to LiCH_2 CMe_3. Sublimation of Ti(CH _2CMe_3)_4 over a substrate heated to 250^ circC results in the chemical vapor

  20. Electromagnetically induced transparency of a plasmonic metamaterial light absorber based on multilayered metallic nanoparticle sheets

    PubMed Central

    Okamoto, Koichi; Tanaka, Daisuke; Degawa, Ryo; Li, Xinheng; Wang, Pangpang; Ryuzaki, Sou; Tamada, Kaoru

    2016-01-01

    In this study, we observed the peak splitting of absorption spectra for two-dimensional sheets of silver nanoparticles due to the electromagnetically induced transparency (EIT) effect. This unique optical phenomenon was observed for the multilayered nanosheets up to 20 layers on a metal substrate, while this phenomenon was not observed on a transparent substrate. The wavelength and intensities of the split peaks depend on the number of layers, and the experimental results were well reproduced by the calculation of the Transfer-Matrix method by employing the effective medium approximation. The Ag nanosheets used in this study can act as a plasmonic metamaterial light absorber, which has a such large oscillator strength. This phenomenon is a fundamental optical property of a thin film on a metal substrate but has never been observed because native materials do not have a large oscillator strength. This new type of EIT effect using a plasmonic metamaterial light absorber presents the potential for the development of future optic and photonic technologies. PMID:27824071

  1. Electromagnetically induced transparency of a plasmonic metamaterial light absorber based on multilayered metallic nanoparticle sheets.

    PubMed

    Okamoto, Koichi; Tanaka, Daisuke; Degawa, Ryo; Li, Xinheng; Wang, Pangpang; Ryuzaki, Sou; Tamada, Kaoru

    2016-11-08

    In this study, we observed the peak splitting of absorption spectra for two-dimensional sheets of silver nanoparticles due to the electromagnetically induced transparency (EIT) effect. This unique optical phenomenon was observed for the multilayered nanosheets up to 20 layers on a metal substrate, while this phenomenon was not observed on a transparent substrate. The wavelength and intensities of the split peaks depend on the number of layers, and the experimental results were well reproduced by the calculation of the Transfer-Matrix method by employing the effective medium approximation. The Ag nanosheets used in this study can act as a plasmonic metamaterial light absorber, which has a such large oscillator strength. This phenomenon is a fundamental optical property of a thin film on a metal substrate but has never been observed because native materials do not have a large oscillator strength. This new type of EIT effect using a plasmonic metamaterial light absorber presents the potential for the development of future optic and photonic technologies.

  2. Electromagnetically induced transparency of a plasmonic metamaterial light absorber based on multilayered metallic nanoparticle sheets

    NASA Astrophysics Data System (ADS)

    Okamoto, Koichi; Tanaka, Daisuke; Degawa, Ryo; Li, Xinheng; Wang, Pangpang; Ryuzaki, Sou; Tamada, Kaoru

    2016-11-01

    In this study, we observed the peak splitting of absorption spectra for two-dimensional sheets of silver nanoparticles due to the electromagnetically induced transparency (EIT) effect. This unique optical phenomenon was observed for the multilayered nanosheets up to 20 layers on a metal substrate, while this phenomenon was not observed on a transparent substrate. The wavelength and intensities of the split peaks depend on the number of layers, and the experimental results were well reproduced by the calculation of the Transfer-Matrix method by employing the effective medium approximation. The Ag nanosheets used in this study can act as a plasmonic metamaterial light absorber, which has a such large oscillator strength. This phenomenon is a fundamental optical property of a thin film on a metal substrate but has never been observed because native materials do not have a large oscillator strength. This new type of EIT effect using a plasmonic metamaterial light absorber presents the potential for the development of future optic and photonic technologies.

  3. Controlling magnetism of MoS2 sheets by embedding transition-metal atoms and applying strain.

    PubMed

    Zhou, Yungang; Su, Qiulei; Wang, Zhiguo; Deng, Huiqiu; Zu, Xiaotao

    2013-11-14

    Prompted by recent experimental achievement of transition metal (TM) atoms substituted in MoS2 nanostructures during growth or saturating existing vacancies (Sun et al., ACS Nano, 2013, 7, 3506; Deepak et al., J. Am. Chem. Soc., 2007, 129, 12549), we explored, via density functional theory, the magnetic properties of a series of 3d TM atoms substituted in a MoS2 sheet, and found that Mn, Fe, Co, Ni, Cu and Zn substitutions can induce magnetism in the MoS2 sheet. The localizing unpaired 3d electrons of TM atoms respond to the introduction of a magnetic moment. Depending on the species of TM atoms, the substituted MoS2 sheet can be a metal, semiconductor or half-metal. Remarkably, the applied elastic strain can be used to control the strength of the spin-splitting of TM-3d orbitals, leading to an effective manipulation of the magnetism of the TM-substituted MoS2 sheet. We found that the magnetic moment of the Mn- and Fe-substituted MoS2 sheets can monotonously increase with the increase of tensile strain, while the magnetic moment of Co-, Ni-, Cu- and Zn-substituted MoS2 sheets initially increases and then decreases with the increase of tensile strain. An instructive mechanism was proposed to qualitatively explain the variation of magnetism with elastic strain. The finding of the magnetoelastic effect here is technologically important for the fabrication of strain-driven spin devices on MoS2 nanostructures, which allows us to go beyond the current scope limited to the spin devices within graphene and BN-based nanostructures.

  4. Alkoxy-Siloxide Metal Complexes: Precursors to Metal Silica, Metal Oxide Silica, and Metal Silicate Materials.

    NASA Astrophysics Data System (ADS)

    Terry, Karl William

    The alkoxy-siloxide complexes M (OSi(O ^{rm t}Bu)_3 ]_4 (M = Ti(1), Zr(2), Hf(3)), were prepared by reaction with their respective metal diethylamides. These compounds readily undergo low-temperature decomposition to their respective metal oxide silica materials rm(MO_2{cdot}4SiO_2). The volatile products of the thermolysis of 2 (ca. 200 ^circC) were isobutylene (11.7 equiv) and water (5.4 equiv). The rm ZrO _2{cdot}4SiO_2 material from the decomposition of 2 at 400^circ C was amorphous until ca. 1100^ circC where crystallization of t-ZrO _2 occurred. After thermolysis to 1500 ^circC, t-ZrO_2 and cristobalite were the major products with minor amounts of m-ZrO_2. The rm HfO_2{cdot}4SiO_2 material from the decomposition of 3 at 400^ circC was amorphous until ca. 1000 ^circC where crystallization of c/t -HfO_2 was observed. Thermolysis to 1460^circC yielded c/t -HfO_2, m-HfO_2, and minor amounts of cristobalite. The crystallization of anatase in the rm TiO_2{cdot }4SiO_2 material from decomposed 1 at 400^circC was apparent after thermolysis to 1000^circC. Thermolysis to 1400^circC gave a mixture of anatase, rutile, and cristobalite. Compound 2 was decomposed in xylenes and yielded a transparent gel which was isolated as a white powder upon drying in vacuuo. The compounds [ Me _2AlOSi(O^{t}Bu)_3] _2 (4) and [( ^{t}BuO)MeAlOSi(O^{t}Bu) _3]_2 (5) were structurally characterized and contain bent and planar rm Al_2O_2 four membered rings, respectively. Both 4 and 5 yield isobutylene upon thermolysis (ca. 200 ^circC) and the crystallization of mullite occurs at 1034^circC and 1017^circC, respectively (by DTA). The solution thermolysis of 4 in refluxing toluene yields an opaque white gel. The crystallization of mullite occurs at 1029^circC (by DTA). The compounds [ CuOSi(O ^{t}Bu)_3]_{n } (6) and [ CuOSi(O ^{t}Bu)_2Ph]_4 (7) were prepared by reaction with [ CuO^{t}Bu]_4. The thermolysis of 6 at 1000^circ C under argon gave Cu^circ and amorphous silica and thermolysis under

  5. VCD Studies on Chiral Characters of Metal Complex Oligomers

    PubMed Central

    Sato, Hisako; Yamagishi, Akihiko

    2013-01-01

    The present article reviews the results on the application of vibrational circular dichroism (VCD) spectroscopy to the study of stereochemical properties of chiral metal complexes in solution. The chiral characters reflecting on the vibrational properties of metal complexes are revealed by measurements of a series of β-diketonato complexes with the help of theoretical calculation. Attention is paid to the effects of electronic properties of a central metal ion on vibrational energy levels or low-lying electronic states. The investigation is further extended to the oligomers of β-diketonato complex units. The induction of chiral structures is confirmed by the VCD spectra when chiral inert moieties are connected with labile metal ions. These results have demonstrated how VCD spectroscopy is efficient in revealing the static and dynamic properties of mononuclear and multinuclear chiral metal complexes, which are difficult to clarify by means of other spectroscopes. PMID:23296273

  6. VCD studies on chiral characters of metal complex oligomers.

    PubMed

    Sato, Hisako; Yamagishi, Akihiko

    2013-01-07

    The present article reviews the results on the application of vibrational circular dichroism (VCD) spectroscopy to the study of stereochemical properties of chiral metal complexes in solution. The chiral characters reflecting on the vibrational properties of metal complexes are revealed by measurements of a series of β-diketonato complexes with the help of theoretical calculation. Attention is paid to the effects of electronic properties of a central metal ion on vibrational energy levels or low-lying electronic states. The investigation is further extended to the oligomers of β-diketonato complex units. The induction of chiral structures is confirmed by the VCD spectra when chiral inert moieties are connected with labile metal ions. These results have demonstrated how VCD spectroscopy is efficient in revealing the static and dynamic properties of mononuclear and multinuclear chiral metal complexes, which are difficult to clarify by means of other spectroscopes.

  7. Synthesis and characterization of some transition metals polymer complexes

    NASA Astrophysics Data System (ADS)

    Masoud, Mamdouh S.; Abdou, Azza E. H.; Ahmed, Wael M.

    2015-09-01

    Co2+, Ni2+, Cu2+, Cr3+, Mn2+ and Fe3+ complexes of Polyacrylamide are prepared and characterized by elemental analyses, IR, UV-Vis spectra, magnetic measurements, and thermal analyses. The data suggests octahedral geometry for all complexes. The thermal behavior of the complexes has been studied applying TG, DTA, and DSC techniques, and the thermodynamic parameters and mechanisms of the decompositions were evaluated. The ΔS# values of the decomposition steps of the metal complexes indicated that the activated fragments have more ordered structure than the undecomposed complexes. The thermal processes proceeded in complicated mechanisms where the bond between the central metal ion and the ligands dissociates after losing 6(C2H5 N) and 6(CO), the metal complexes are ended with metal as a final product. Viscosity and Shale instability using liner swell meter were carried out. Comparisons of the experimental and theoretical IR spectra were also carried out besides some other theoretical calculations.

  8. Metal complexes of quinolone antibiotics and their applications: an update.

    PubMed

    Uivarosi, Valentina

    2013-09-11

    Quinolones are synthetic broad-spectrum antibiotics with good oral absorption and excellent bioavailability. Due to the chemical functions found on their nucleus (a carboxylic acid function at the 3-position, and in most cases a basic piperazinyl ring (or another N-heterocycle) at the 7-position, and a carbonyl oxygen atom at the 4-position) quinolones bind metal ions forming complexes in which they can act as bidentate, as unidentate and as bridging ligand, respectively. In the polymeric complexes in solid state, multiple modes of coordination are simultaneously possible. In strongly acidic conditions, quinolone molecules possessing a basic side nucleus are protonated and appear as cations in the ionic complexes. Interaction with metal ions has some important consequences for the solubility, pharmacokinetics and bioavailability of quinolones, and is also involved in the mechanism of action of these bactericidal agents. Many metal complexes with equal or enhanced antimicrobial activity compared to the parent quinolones were obtained. New strategies in the design of metal complexes of quinolones have led to compounds with anticancer activity. Analytical applications of complexation with metal ions were oriented toward two main directions: determination of quinolones based on complexation with metal ions or, reversely, determination of metal ions based on complexation with quinolones.

  9. Direct measurement of sheet resistance Rsquare in cuprate systems: evidence of a fermionic scenario in a metal-insulator transition.

    PubMed

    Orgiani, P; Aruta, C; Balestrino, G; Born, D; Maritato, L; Medaglia, P G; Stornaiuolo, D; Tafuri, F; Tebano, A

    2007-01-19

    The metal-insulator transition (MIT) has been studied in Ba(0.9)Nd(0.1)CuO(2+x)/CaCuO2 ultrathin cuprate structures. Such structures allow for the direct measurement of the 2D sheet resistance R( square), eliminating ambiguity in the definition of the effective thickness of the conducting layer in high temperature superconductors. The MIT occurs at room temperature for experimental values of R(square) close to the 25.8 kOmega universal quantum resistance. All data confirm the assumption that each CaCuO2 layer forms a 2D superconducting sheet within the superconducting block, which can be described as weak-coupled equivalent sheets in parallel.

  10. Technology maturation project on optimization of sheet metal forming of aluminum for use in transportation systems

    NASA Astrophysics Data System (ADS)

    Johnson, Ken I.; Smith, Mark T.; Lavender, Curt A.; Khalell, Mohammad A.

    1994-10-01

    Using aluminum instead of steel in transportation systems could dramatically reduce the weight of vehicles, an effective way of decreasing energy consumption and emissions. The current cost of sheet metal formed (SMF) aluminum alloys (about $4 per pound) and the relatively long forming times of current materials are serious drawbacks to the widespread use of SMF in industry. The interdependence of materials testing and model development is critical to optimizing SMF since the current process is conducted in a heated, pressurized die where direct measurement of critical SMF parameters is extremely difficult. Numerical models provide a means of tracking the forming process, allowing the applied gas pressure to be adjusted to maintain the optimum SMF behavior throughout the forming process. Thus, models can help produce the optimum SMF component in the least amount of time. The Pacific Northwest Laboratory is integrating SMF model development with research in improved aluminum alloys for SMF. The objectives of this research are: develop and characterize competitively priced aluminum alloys for SMF applications in industry; improve numerical models to accurately predict the optimum forming cycle for reduced forming time and improved quality; and verify alloy performance and model accuracy with forming tests conducted in PNL's Superplastic Forming User Facility. The activities performed in this technology maturation project represent a critical first step in achieving these objectives through cooperative research among industry, PNL, and universities.

  11. Springback Simulation and Tool Surface Compensation Algorithm for Sheet Metal Forming

    SciTech Connect

    Shen Guozhe; Hu Ping; Zhang Xiangkui; Chen Xiaobin; Li Xiaoda

    2005-08-05

    Springback is an unquenchable forming defect in the sheet metal forming process. How to calculate springback accurately is a big challenge for a lot of FEA software. Springback compensation makes the stamped final part accordant with the designed part shape by modifying tool surface, which depends on the accurate springback amount. How ever, the meshing data based on numerical simulation is expressed by nodes and elements, such data can not be supplied directly to tool surface CAD data. In this paper, a tool surface compensation algorithm based on numerical simulation technique of springback process is proposed in which the independently developed dynamic explicit springback algorithm (DESA) is used to simulate springback amount. When doing the tool surface compensation, the springback amount of the projected point can be obtained by interpolation of the springback amount of the projected element nodes. So the modified values of tool surface can be calculated reversely. After repeating the springback and compensation calculations for 1{approx}3 times, the reasonable tool surface mesh is gained. Finally, the FEM data on the compensated tool surface is fitted into the surface by CAD modeling software. The examination of a real industrial part shows the validity of the present method.

  12. Audio signal analysis for tool wear monitoring in sheet metal stamping

    NASA Astrophysics Data System (ADS)

    Ubhayaratne, Indivarie; Pereira, Michael P.; Xiang, Yong; Rolfe, Bernard F.

    2017-02-01

    Stamping tool wear can significantly degrade product quality, and hence, online tool condition monitoring is a timely need in many manufacturing industries. Even though a large amount of research has been conducted employing different sensor signals, there is still an unmet demand for a low-cost easy to set up condition monitoring system. Audio signal analysis is a simple method that has the potential to meet this demand, but has not been previously used for stamping process monitoring. Hence, this paper studies the existence and the significance of the correlation between emitted sound signals and the wear state of sheet metal stamping tools. The corrupting sources generated by the tooling of the stamping press and surrounding machinery have higher amplitudes compared to that of the sound emitted by the stamping operation itself. Therefore, a newly developed semi-blind signal extraction technique was employed as a pre-processing technique to mitigate the contribution of these corrupting sources. The spectral analysis results of the raw and extracted signals demonstrate a significant qualitative relationship between wear progression and the emitted sound signature. This study lays the basis for employing low-cost audio signal analysis in the development of a real-time industrial tool condition monitoring system.

  13. A simple method for understanding the triangular growth patterns of transition metal dichalcogenide sheets

    SciTech Connect

    Zhu, Siya; Wang, Qian

    2015-10-15

    Triangular nanoflake growth patterns have been commonly observed in synthesis of transition metal dichalcogenide sheets and their hybrid structures. Triangular nanoflakes not only show exceptional properties, but also can serve as building blocks for two or three dimensional structures. In this study, taking the MoS{sub 2} system as a test case, we propose a Matrix method to understand the mechanism of such unique growth pattern. Nanoflakes with different edge types are mathematically described with configuration matrices, and the total formation energy is calculated as the sum of the edge formation energies and the chemical potentials of sulfur and molybdenum. Based on energetics, we find that three triangular patterns with the different edge configurations are energetically more favorable in different ranges of the chemical potential of sulfur, which are in good agreement with experimental observations. Our algorithm has high efficiency and can deal with nanoflakes in microns which are beyond the ability of ab-initio method. This study not only elucidates the mechanism of triangular nanoflake growth patterns in experiment, but also provides a clue to control the geometric configurations in synthesis.

  14. Editorial input for the right price: tobacco industry support for a sheet metal indoor air quality manual.

    PubMed

    Campbell, Richard; Balbach, Edith

    2013-01-01

    Following legal action in the 1990s, internal tobacco industry documents became public, allowing unprecedented insight into the industry's relationships with outside organizations. During the 1980s and 1990s, the National Energy Management Institute (NEMI), established by the Sheet Metal Workers International Association and the Sheet Metal and Air Conditioning Contractors' National Association, (SMACNA) received tobacco industry funding to establish an indoor air quality services program. But the arrangement also required NEMI to serve as an advocate for industry efforts to defeat indoor smoking bans by arguing that ventilation was a more appropriate solution to environmental tobacco smoke. Drawing on tobacco industry documents, this paper describes a striking example of the ethical compromises that accompanied NEMI's collaboration with the tobacco industry, highlighting the solicitation of tobacco industry financial support for a SMACNA indoor air quality manual in exchange for sanitizing references to the health impact of environmental tobacco smoke prior to publication.

  15. Density functional analysis of gaseous molecules adsorbed on metal ion/defective nano-sheet graphene

    NASA Astrophysics Data System (ADS)

    Deng, Jin-Pei; Chuang, Wen-Hua; Tai, Chin-Kuen; Kao, Hsien-Chang; Pan, Jiunn-Hung; Wang, Bo-Cheng

    2016-11-01

    Density functional theory was applied to calculate the adsorption property of metal/hexa-vacancy defective graphene (denoted as HDG-M, M: Fe2+, Co2+, Ni2+, Cu2+ and Zn2+) with O- and N-dopants. We investigate the adsorption properties of these complexes between gaseous molecules and HDG-M. Our results show that HDG-Cu has a high selectivity for O2, but HDG-Fe has a good ability to capture many gases such as CO, NO and O2. Our calculations could provide useful information for designing new graphene-based adsorbents to remove undesired gases, which may poison the metal catalysts in reaction processes.

  16. Evaluation of local and integral magnitudes in metal sheets inductive levitation device by FEM electromagnetic field modeling

    SciTech Connect

    Fireteanu, V.; Craiu, O.; Curiac, R.

    1996-05-01

    This paper presents a numerical computation of a device for the horizontal casting of the inductive levitated metallic sheets. Local and integral magnitudes of electromagnetic field values are computed by means of FEM, using the FLUX-2D software and the dedicated program LEVITA. The influences of the supply frequency, magnetic saturation, and device configuration on the levitation force, induced power and transverse variation of the levitation force density are studied. Some experimental proof of the calculated magnitudes is also presented.

  17. A new non-contact approach for the measurement and uniformity evaluation of coating thickness for sheet metal.

    PubMed

    Qiu, Zixue; Zheng, Tianchi; Wan, Liping; Lu, Guan; Shao, Jianxin; Yuan, Jiang

    2017-01-01

    To realize the automatic measurement and uniformity evaluation of the coating thickness for sheet metal, a new non-contact detection method for coating thickness was proposed based on a double laser probe and mechanical servo system. Non-contact measurement of coating thickness can be achieved by differential measurement principle of double laser probe, and the influences of sheet metal's Z position changes and platform's vibration on the measurement results can be removed by this method. A new coating thickness evaluation algorithm by integrating the least squares principle and cubic spline interpolation was given, which can fit the discrete thickness data into visual and accurate 3D graphics; and the measurement accuracy was evaluated based on grey theory, solving the problem of low accuracy by using limited measurement data to evaluate the thickness uniformity of an entire sheet metal. The stability and reliability of the system are verified by experiments, and the measurement results of the specimen show that the measurement uncertainty is 0.016 μm and the maximum range of the uniformity evaluation result is 1.4 μm.

  18. Design of a mechanical test to characterize sheet metals - Optimization using B-splines or cubic splines

    NASA Astrophysics Data System (ADS)

    Souto, Nelson; Thuillier, Sandrine; Andrade-Campos, A.

    2016-10-01

    Nowadays, full-field measurement methods are largely used to acquire the strain field developed by heterogeneous mechanical tests. Recent material parameters identification strategies based on a single heterogeneous test have been proposed considering that an inhomogeneous strain field can lead to a more complete mechanical characterization of the sheet metals. The purpose of this work is the design of a heterogeneous test promoting an enhanced mechanical behavior characterization of thin metallic sheets, under several strain paths and strain amplitudes. To achieve this goal, a design optimization strategy finding the appropriate specimen shape of the heterogeneous test by using either B-Splines or cubic splines was developed. The influence of using approximation or interpolation curves, respectively, was investigated in order to determine the most effective approach for achieving a better shape design. The optimization process is guided by an indicator criterion which evaluates, quantitatively, the strain field information provided by the mechanical test. Moreover, the design of the heterogeneous test is based on the resemblance with the experimental reality, since a rigid tool leading to uniaxial loading path is used for applying the displacement in a similar way as universal standard testing machines. The results obtained reveal that the optimization strategy using B-Splines curve approximation led to a heterogeneous test providing larger strain field information for characterizing the mechanical behavior of sheet metals.

  19. Transition Metal and Vacancy Defect Complexes in Phosphorene

    NASA Astrophysics Data System (ADS)

    Kabir, Mukul; Babar, Rohit

    Inducing magnetic moment in otherwise nonmagnetic two-dimensional semiconducting materials is the first step to design spintronic material. Here, we study the adsorption of transition-metals on pristine and defected phosphorene, within density functional theory. We predict that increased transition-meal diffusivity on the pristine phosphorene would hinder controlled magnetism. In contrast, point-defects anchor the transiton-metal to reduce metal diffusivity. The di-vacancy complex is more important in this context due to their increased thermodynamic stability over the mono-vacancy. For most cases, the defect-transition metal complexes retain the intrinsic semiconducting properties, and induce a local moment. We provide a simple microscopic model which describe the local moment of these transition metal and defect complexes.

  20. Preparation and Characterization of a Hydrophobic Metal-Organic Framework Membrane Supported on Thin Porous Metal Sheet

    SciTech Connect

    Liu, Jian; Canfield, Nathan L.; Liu, Wei

    2016-02-29

    A hydrophobic metal-organic framework (MOF) UiO-66-CH3 is prepared and its solvothermal stability is investigated in comparison to UiO-66. It is confirmed that the MOF stability is enhanced by introduction of the two methyl groups, while the water adsorption is reduced. Given its hydrophobicity and stability, UiO-66-CH3 is proposed as an attractive membrane material for gas separation under moisture conditions. The UiO-66-CH3 membrane is prepared on a 50µm-thin porous Ni support sheet for the first time by use of a secondary growth method. It is found that uniform seed coating on the support is necessary to form a continuous membrane. In addition to growth time and temperature, presence of a modulator in the growth solution is found to be useful for controlling hydrothermal membrane growth on the seeded support. A dense, inter-grown membrane layer is formed by 24-h growth over a temperature range from 120 oC to 160 oC. The membrane surface comprises 500 nm octahedral crystals, which are supposed to grow out of the original 100 nm spherical seeding crystals. The separation characteristics of resulting membranes are tested with pure CO2, air, CO2/air mixture, and humid CO2/air mixture. CO2 permeance as high as 1.9E-06 mol/m2/s/Pa at 31oC is obtained. Unlike the hydrophilic zeolite membranes, CO2 permeation through this membrane is not blocked by the presence of water vapor in the feed gas. The results suggest that this MOF framework is a promising membrane material worth to be further investigated for separation of CO2 and other small molecules from humid gas mixtures.

  1. Porphyrins and metal complexes thereof having haloalkyl side chains

    DOEpatents

    Wijesekera, T.; Lyons, J.E.; Ellis, P.E. Jr.; Bhinde, M.V.

    1997-03-04

    Transition metal complexes of meso-haloalkylporphyrins, wherein the haloalkyl groups contain 2 to 8 carbon atoms have been found to be highly effective catalysts for oxidation of alkanes and for the decomposition of hydroperoxides. 7 figs.

  2. Porphyrins and metal complexes thereof having haloalkyl side chains

    DOEpatents

    Wijesekera, Tilak; Lyons, James E.; Ellis, Jr., Paul E.; Bhinde, Manoj V.

    1997-01-01

    Transition metal complexes of meso-haloalkylporphyrins, wherein the haloalkyl groups contain 2 to 8 carbon atoms have been found to be highly effective catalysts for oxidation of alkanes and for the decomposition of hydroperoxides.

  3. N-Heterocyclic carbene metal complexes in medicinal chemistry.

    PubMed

    Oehninger, Luciano; Rubbiani, Riccardo; Ott, Ingo

    2013-03-14

    Metal complexes with N-heterocyclic carbene (NHC) ligands are widely used in chemistry due to their catalytic properties and applied for olefin metathesis among other reactions. The enhanced application of this type of organometallics has over the last few years also triggered a steadily increasing number of studies in the fields of medicinal chemistry, which take advantage of the fascinating chemical properties of these complexes. In fact it has been demonstrated that metal NHC complexes can be used to develop highly efficient metal based drugs with possible applications in the treatment of cancer or infectious diseases. Complexes of silver and gold have been biologically evaluated most frequently but also platinum or other transition metals have demonstrated promising biological properties.

  4. A Simple Method for Drawing Chiral Mononuclear Octahedral Metal Complexes

    ERIC Educational Resources Information Center

    Mohamadou, Aminou; Haudrechy, Arnaud

    2008-01-01

    Octahedral transition-metal complexes are involved in a number of reactions and octahedral coordination geometry, frequently observed for metallic centers, includes important topographical stereochemistry. Depending on the number and nature of different ligands, octahedral coordination units with at least two different monodentate ligands give…

  5. Transition metal complexes of isonicotinic acid (2-hydroxybenzylidene)hydrazide

    NASA Astrophysics Data System (ADS)

    Abou-Melha, Khlood S.

    2008-06-01

    A new series of transition metal complexes of Schiff base isonicotinic acid (2-hydroxybenzylidene)hydrazide, HL, have been synthesized. The Schiff base reacted with Cu(II), Ni(II), Co(II), Mn(II), Fe(III) and UO 2(II) ions as monobasic tridentate ligand to yield mononuclear complexes of 1:2 (metal:ligand) except that of Cu(II) which form complex of 1:1 (metal:ligand). The ligand and its metal complexes were characterized by elemental analyses, IR, UV-vis, mass and 1H NMR spectra, as well as magnetic moment, conductance measurements, and thermal analyses. All complexes have octahedral configurations except Cu(II) complex which has an extra square planar geometry distorted towards tetrahedral. While, the UO 2(II) complex has its favour hepta-coordination. The ligand and its metal complexes were tested against one strain Gram +ve bacteria ( Staphylococcus aureus), Gram -ve bacteria (Escherichia coli) , and Fungi ( Candida albicans). The tested compounds exhibited higher antibacterial activities.

  6. Transition metal complexes of isonicotinic acid (2-hydroxybenzylidene)hydrazide.

    PubMed

    Abou-Melha, Khlood S

    2008-06-01

    A new series of transition metal complexes of Schiff base isonicotinic acid (2-hydroxybenzylidene)hydrazide, HL, have been synthesized. The Schiff base reacted with Cu(II), Ni(II), Co(II), Mn(II), Fe(III) and UO2(II) ions as monobasic tridentate ligand to yield mononuclear complexes of 1:2 (metal:ligand) except that of Cu(II) which form complex of 1:1 (metal:ligand). The ligand and its metal complexes were characterized by elemental analyses, IR, UV-vis, mass and 1H NMR spectra, as well as magnetic moment, conductance measurements, and thermal analyses. All complexes have octahedral configurations except Cu(II) complex which has an extra square planar geometry distorted towards tetrahedral. While, the UO2(II) complex has its favour hepta-coordination. The ligand and its metal complexes were tested against one strain Gram +ve bacteria (Staphylococcus aureus), Gram -ve bacteria (Escherichia coli), and Fungi (Candida albicans). The tested compounds exhibited higher antibacterial activities.

  7. Heavy metal music meets complexity and sustainability science.

    PubMed

    Angeler, David G

    2016-01-01

    This paper builds a bridge between heavy metal music, complexity theory and sustainability science to show the potential of the (auditory) arts to inform different aspects of complex systems of people and nature. The links are described along different dimensions. This first dimension focuses on the scientific aspect of heavy metal. It uses complex adaptive systems theory to show that the rapid diversification and evolution of heavy metal into multiple subgenres leads to a self-organizing and resilient socio-musicological system. The second dimension builds on the recent use of heavy metal as a critical thinking model and educational tool, emphasizing the artistic component of heavy metal and its potential to increase people's awareness of environmental sustainability challenges. The relationships between metal, complexity theory and sustainability are first discussed independently to specifically show mechanistic links and the reciprocal potential to inform one domain (science) by the other (metal) within these dimensions. The paper concludes by highlighting that these dimensions entrain each other within a broader social-cultural-environmental system that cannot be explained simply by the sum of independent, individual dimensions. Such a unified view embraces the inherent complexity with which systems of people and nature interact. These lines of exploration suggest that the arts and the sciences form a logical partnership. Such a partnership might help in endeavors to envision, understand and cope with the broad ramifications of sustainability challenges in times of rapid social, cultural, and environmental change.

  8. Experimental Studies on Flexible Forming of Sheet Metals Assisted by Magnetic Force Transfer Medium

    NASA Astrophysics Data System (ADS)

    Li, Feng; Zhou, Fu Jian; Wang, Mo Nan; Xu, Peng; Jin, Cheng Chuang

    2016-08-01

    To improve the thickness uniformity and increase the forming limit of sheets to enhance their overall quality, a magnetorheological fluid (MRF) was injected into the punch cavity to act as the force transfer medium and fulfill the function of flexible pressing during the sheet bulging process. The rheological properties of the MRF were changed under the influence of a magnetic field produced by loading different currents, which allowed variation of stress states and deformation modes in the 0.75-mm-thick 304 stainless steel sheets. With increasing current (up to 3.5 A), the sheet-forming limit increased by 16.13% at most, and the fracture morphology experienced a certain change. Additionally, both the bulge height and the wall thickness distribution had obvious changes with a punch stroke of 10 mm. According to the experimental analysis, the MRF can be used successfully as a pressure-carrying medium in the sheet forming process.

  9. Endoscopic fringe projection for in-situ inspection of a sheet-bulk metal forming process

    NASA Astrophysics Data System (ADS)

    Matthias, Steffen; Kästner, Markus; Reithmeier, Eduard

    2015-05-01

    Sheet-bulk metal forming is a new production process capable of performing deep-drawing and massive forming steps in a single operation. However, due to the high forming forces of the forming process, continuous process control is required in order to detect wear on the forming tool before production quality is impacted. To be able to measure the geometry of the forming tool in the limited space of forming presses, a new inspection system is being developed within the SFB/TR 73 collaborative research center. In addition to the limited space, the process restricts the amount of time available for inspection. Existing areal optical measurement systems suffer from shadowing when measuring the tool's inner elements, as they cannot be placed in the limited space next to the tool, while tactile measurement systems cannot meet the time restrictions for measuring the areal geometries. The new inspection system uses the fringe projection optical measurement principle to capture areal geometry data from relevant parts of the forming tool in short time. Highresolution image fibers are used to connect the system's compact sensor head to a base unit containing both camera and projector of the fringe projection system, which can be positioned outside of the moving parts of the press. To enable short measurement times, a high intensity laser source is used in the projector in combination with a digital micro-mirror device. Gradient index lenses are featured in the sensor head to allow for a very compact design that can be used in the narrow space above the forming tool inside the press. The sensor head is attached to an extended arm, which also guides the image fibers to the base unit. A rotation stage offers the possibility to capture measurements of different functional elements on the circular forming tool by changing the orientation of the sensor head next to the forming tool. During operation of the press, the arm can be travelled out of the moving parts of the forming press

  10. Plant rhamnogalacturonan II complexation of heavy metal cations

    DOEpatents

    O`Neill, M.A.; Pellerin, P.J.M.; Warrenfeltz, D.; Vidal, S.; Darvill, A.G.; Albersheim, P.

    1999-03-02

    The present invention provides rhamnogalacturonan-II (RG-II) and relates to its ability to complex specific multivalent heavy metal cations. In the presence of boric acid, RG-II monomers form dimers that are cross-linked by a borate ester. The yield of such borate ester cross-linked dimers of RG-II is enhanced in the presence of specific heavy metal cations. The present invention further relates to the utility of RG-II in assays for the detection of specific heavy metal contamination; as a reagent useful in the removal of specific heavy metal cations contaminating foods and liquids, for example, fish, wines, etc.; as a pharmaceutical composition useful as an antidote in specific heavy metal cation poisoning; as a treatment for the detoxification of specific heavy metal cations from blood and/or tissues; and in a method of remediation of waters and soils contaminated with specific heavy metal cations. 15 figs.

  11. Plant rhamnogalacturonan II complexation of heavy metal cations

    DOEpatents

    O'Neill, Malcolm A.; Pellerin, Patrice J. M.; Warrenfeltz, Dennis; Vidal, Stephane; Darvill, Alan G.; Albersheim, Peter

    1999-01-01

    The present invention provides rhamnogalacturonan-II (RG-II) and relates to its ability to complex specific multivalent heavy metal cations. In the presence of boric acid, RG-II monomers form dimers that are cross-linked by a borate ester. The yield of such borate ester cross-linked dimers of RG-II is enhanced in the presence of specific heavy metal cations. The present invention further relates to the utility of RG-II in assays for the detection of specific heavy metal contamination; as a reagent useful in the removal of specific heavy metal cations contaminating foods and liquids, for example, fish, wines, etc.; as a pharmaceutical composition useful as an antidote in specific heavy metal cation poisoning; as a treatment for the detoxification of specific heavy metal cations from blood and/or tissues; and in a method of remediation of waters and soils contaminated with specific heavy metal cations.

  12. Preparation of porphyrins and their metal complexes

    DOEpatents

    Ellis, Jr., Paul E.; Langdale, Wayne A.

    1997-01-01

    A hydroxyl-containing pyrrolic compound having a hydroxyl group or a hydroxyl-containing group in the 2-position, optionally substituted in the beta positions, is condensed in an acidified two immiscible phase solvent system to produce excellent yields of the corresponding porphyrin or metal porphyrin.

  13. Preparation of porphyrins and their metal complexes

    DOEpatents

    Ellis, P.E. Jr.; Langdale, W.A.

    1997-08-19

    A hydroxyl-containing pyrrolic compound having a hydroxyl group or a hydroxyl-containing group in the 2-position, optionally substituted in the beta positions, is condensed in an acidified two immiscible phase solvent system to produce excellent yields of the corresponding porphyrin or metal porphyrin.

  14. Aeromagnetic evidence for a volcanic caldera(?) complex beneath the divide of the West Antarctic Ice Sheet

    USGS Publications Warehouse

    Behrendt, John C.; Finn, C.A.; Blankenship, D.; Bell, R.E.

    1998-01-01

    A 1995-96 aeromagnetic survey over part of the Sinuous Ridge (SR) beneath the West Antarctic Ice Sheet (WAIS) divide shows a 70-km diameter circular pattern of 400-1200-nT anomalies suggesting one of the largest volcanic caldera(?) complexes on earth. Radar-ice-sounding (RIS) shows the northern part of this pattern overlies the SR, and extends south over the Bentley Subglacial Trench (BST). Modeled sources of all but one the caldera(?) anomalies are at the base of <1-2-km thick ice and their volcanic edifices have been glacially removed. The exception is a 700-m high, 15-km wide 'volcano' producing an 800-nT anomaly over the BST. 'Intrusion' of this 'volcano' beneath 3 km of ice probably resulted in pillow basalt rather than easily removed hyaloclastite erupted beneath thinner ice. The background area (-300 to -500-nT) surrounding the caldera(?) is possibly caused by a shallow Curie isotherm. We suggest uplift of the SR forced the advance of the WAIS.A 1995-96 aeromagnetic survey over part of the Sinuous Ridge (SR) beneath the West Antarctic Ice Sheet (WAIS) divide shows a 70-km diameter circular pattern of 400-1200-nT anomalies suggesting one of the largest volcanic caldera(?) complexes on earth. Radar-ice-sounding (RIS) shows the northern part of this pattern overlies the SR, and extends south over the Bentley Subglacial Trench (BST). Modeled sources of all but one the caldera(?) anomalies are at the base of < 1-2-km thick ice and their volcanic edifices have been glacially removed. The exception is a 700-m high, 15-km wide 'volcano' producing an 800-nT anomaly over the BST. 'Intrusion' of this 'volcano' beneath 3 km of ice probably resulted in pillow basalt rather than easily removed hyaloclastite erupted beneath thinner ice. The background area (-300 to -500-nT) surrounding the caldera(?) is possibly caused by a shallow Curie isotherm. We suggest uplift of the SR forced the advance of the WAIS.

  15. Paradigm Change: Alternate Approaches to Constitutive and Necking Models for Sheet Metal Forming

    NASA Astrophysics Data System (ADS)

    Stoughton, Thomas B.; Yoon, Jeong Whan

    2011-08-01

    This paper reviews recent work proposing paradigm changes for the currently popular approach to constitutive and failure modeling, focusing on the use of non-associated flow rules to enable greater flexibility to capture the anisotropic yield and flow behavior of metals using less complex functions than those needed under associated flow to achieve that same level of fidelity to experiment, and on the use of stress-based metrics to more reliably predict necking limits under complex conditions of non-linear forming. The paper discusses motivating factors and benefits in favor of both associated and non-associated flow models for metal forming, including experimental, theoretical, and practical aspects. This review is followed by a discussion of the topic of the forming limits, the limitations of strain analysis, the evidence in favor of stress analysis, the effects of curvature, bending/unbending cycles, triaxial stress conditions, and the motivation for the development of a new type of forming limit diagram based on the effective plastic strain or equivalent plastic work in combination with a directional parameter that accounts for the current stress condition.

  16. Paradigm Change: Alternate Approaches to Constitutive and Necking Models for Sheet Metal Forming

    SciTech Connect

    Stoughton, Thomas B.; Yoon, Jeong Whan

    2011-08-22

    This paper reviews recent work proposing paradigm changes for the currently popular approach to constitutive and failure modeling, focusing on the use of non-associated flow rules to enable greater flexibility to capture the anisotropic yield and flow behavior of metals using less complex functions than those needed under associated flow to achieve that same level of fidelity to experiment, and on the use of stress-based metrics to more reliably predict necking limits under complex conditions of non-linear forming. The paper discusses motivating factors and benefits in favor of both associated and non-associated flow models for metal forming, including experimental, theoretical, and practical aspects. This review is followed by a discussion of the topic of the forming limits, the limitations of strain analysis, the evidence in favor of stress analysis, the effects of curvature, bending/unbending cycles, triaxial stress conditions, and the motivation for the development of a new type of forming limit diagram based on the effective plastic strain or equivalent plastic work in combination with a directional parameter that accounts for the current stress condition.

  17. Metal-metal multiple bonding in C3-symmetric bimetallic complexes of the first row transition metals.

    PubMed

    Krogman, Jeremy P; Thomas, Christine M

    2014-05-25

    Metal-metal multiple bonds have been an intense area of focus in inorganic chemistry for many decades as a result of their fundamentally interesting bonding properties, as well as their potential applications in multielectron transfer and small molecule activation processes. Much of what is known in this field revolves around 2nd and 3rd row transition metals, with fundamental knowledge lacking in the area of bonds between elements of the first transition series. The smaller size and tendency of first row ions to adopt high-spin electron configurations weaken metal-metal interactions and serve to complicate the interpretation of the electronic structure and bonding in bimetallic species containing first row transition metals. Furthermore, traditional tetragonal "paddlewheel" complexes dominate the metal-metal multiple bond literature, and only recently have researchers begun to take advantage of the weaker ligand field in three-fold symmetric bimetallic complexes to encourage more favourable metal-metal bonding interactions. In the past 5 years, several research groups have exploited three-fold symmetric frameworks to investigate new trends in metal-metal bonding involving the first row transition metals. This feature article serves to highlight recent achievements in this area and to use C3-symmetric systems as a model to better understand the fundamental aspects of multiple bonds featuring first row transition metals.

  18. Metal Complexes of Diisopropylthiourea: Synthesis, Characterization and Antibacterial Studies

    PubMed Central

    Ajibade, Peter A.; Zulu, Nonkululeko H.

    2011-01-01

    Co(II), Cu(II), Zn(II) and Fe(III) complexes of diisopropylthiourea have been synthesized and characterized by elemental analyses, molar conductivity, magnetic susceptibility, FTIR and electronic spectroscopy. The compounds are non-electrolytes in solution and spectroscopic data of the complexes are consistent with 4-coordinate geometry for the metal(II) complexes and six coordinate octahedral for Fe(III) complex. The complexes were screened for their antibacterial activities against six bacteria: Escherichia coli, Pseudomonas auriginosa, Klebsiella pneumoniae, Bacillus cereus, Staphylococcus aureus and Bacillus pumilus. The complexes showed varied antibacterial activities and their minimum inhibitory concentrations (MICs) were determined. PMID:22072941

  19. Metal complexes of diisopropylthiourea: synthesis, characterization and antibacterial studies.

    PubMed

    Ajibade, Peter A; Zulu, Nonkululeko H

    2011-01-01

    Co(II), Cu(II), Zn(II) and Fe(III) complexes of diisopropylthiourea have been synthesized and characterized by elemental analyses, molar conductivity, magnetic susceptibility, FTIR and electronic spectroscopy. The compounds are non-electrolytes in solution and spectroscopic data of the complexes are consistent with 4-coordinate geometry for the metal(II) complexes and six coordinate octahedral for Fe(III) complex. The complexes were screened for their antibacterial activities against six bacteria: Escherichia coli, Pseudomonas auriginosa, Klebsiella pneumoniae, Bacillus cereus, Staphylococcus aureus and Bacillus pumilus. The complexes showed varied antibacterial activities and their minimum inhibitory concentrations (MICs) were determined.

  20. Effect of Individual Layer Shape on the Mechanical Properties of Dissimilar Al Alloys Laminated Metal Composite Sheets

    NASA Astrophysics Data System (ADS)

    Chen, Zejun; Wu, Xia; Hu, Hongbo; Chen, Quanzhong; Liu, Qing

    2014-03-01

    For the dissimilar laminated metal composite sheets (LMCS) fabricated by roll bonding technology, the great differences of mechanical properties between the constituent metals lead to the non-uniform deformation and individual layer necking. The individual layer shape affects the mechanical properties and microstructure of dissimilar LMCS. The Al/Al alloy (1100/7075) LMCS with the same thickness and ratio of dissimilar metals, but different individual layer shapes, have been successfully fabricated by hot accumulative roll bonding in conjunction with cold rolling technology. Some effective methods (such as sheet crown, warp degree, and slant angle) were presented to quantitatively evaluate the individual layer shape and necking of constituent metals. The microstructure and mechanical properties of 1100/7075 LMCS with different individual layer shapes were investigated. The effects of bonding interface on the mechanical properties were obtained based on the assessment of individual layer shapes and necking. The strength and elongation of LMCS decrease with the increase of variation of individual layer shapes and necking when the number of layers keeps constant. The research results offer some theoretical guides and references for adjusting the control measures of compatibility deformation, optimizing the hot roll bonding technologies, and designing the novel high-performance dissimilar LMCS.

  1. Designing the Color of Hot-Dip Galvanized Steel Sheet Through Destructive Light Interference Using a Zn-Ti Liquid Metallic Bath

    NASA Astrophysics Data System (ADS)

    Levai, Gabor; Godzsák, Melinda; Török, Tamas I.; Hakl, Jozsef; Takáts, Viktor; Csik, Attila; Vad, Kalman; Kaptay, George

    2016-07-01

    The color of hot-dip galvanized steel sheet was adjusted in a reproducible way using a liquid Zn-Ti metallic bath, air atmosphere, and controlling the bath temperature as the only experimental parameter. Coloring was found only for samples cooled in air and dipped into Ti-containing liquid Zn. For samples dipped into a 0.15 wt pct Ti-containing Zn bath, the color remained metallic (gray) below a 792 K (519 °C) bath temperature; it was yellow at 814 K ± 22 K (541 °C ± 22 °C), violet at 847 K ± 10 K (574 °C ± 10 °C), and blue at 873 K ± 15 K (600 °C ± 15 °C). With the increasing bath temperature, the thickness of the adhered Zn-Ti layer gradually decreased from 52 to 32 micrometers, while the thickness of the outer TiO2 layer gradually increased from 24 to 69 nm. Due to small Al contamination of the Zn bath, a thin (around 2 nm) alumina-rich layer is found between the outer TiO2 layer and the inner macroscopic Zn layer. It is proven that the color change was governed by the formation of thin outer TiO2 layer; different colors appear depending on the thickness of this layer, mostly due to the destructive interference of visible light on this transparent nano-layer. A complex model was built to explain the results using known relationships of chemical thermodynamics, adhesion, heat flow, kinetics of chemical reactions, diffusion, and optics. The complex model was able to reproduce the observations and allowed making predictions on the color of the hot-dip galvanized steel sample, as a function of the following experimental parameters: temperature and Ti content of the Zn bath, oxygen content, pressure, temperature and flow rate of the cooling gas, dimensions of the steel sheet, velocity of dipping the steel sheet into the Zn-Ti bath, residence time of the steel sheet within the bath, and the velocity of its removal from the bath. These relationships will be valuable for planning further experiments and technologies on color hot-dip galvanization of steel

  2. On the increase of geometric accuracy with the help of stiffening elements for robot-based incremental sheet metal forming

    NASA Astrophysics Data System (ADS)

    Thyssen, Lars; Seim, Patrick; Störkle, Denis D.; Kuhlenkötter, Bernd

    2016-10-01

    This paper describes new developments in an incremental, robot-based sheet metal forming process (`Roboforming') for the production of sheet metal components for small lot sizes and prototypes. The incremental sheet forming (ISF) offers high geometrical form flexibility without the need of any part-dependent tools. To transfer the ISF to industrial applications, it is necessary to respond to the still existing constraints, e.g. the low geometrical accuracy. Especially the subsequent deformation resulting from the interaction of differently shaped elements causes geometrical deviations, which are limiting the scope of formable parts. The impact of the resulting forming forces will vary according to the shape of the individual elements. For this, the paper proposes and examines a new approach to stabilize the geometrical accuracy without losing the universal approach of Roboforming by inserting stiffening elements. Those elements with varying cross-sections at the initial area of various orientations must be examined on their stabilizing or subsequent distorting impact. Especially the different impacts of the subsequent forming of stiffness features in contrast to the direct forming are studied precisely.

  3. Metal complexes of substituted Gable porphyrins as oxidation catalysts

    DOEpatents

    Lyons, J.E.; Ellis, P.E. Jr.; Wagner, R.W.

    1996-01-02

    Transition metal complexes of Gable porphyrins are disclosed having two porphyrin rings connected through a linking group, and having on the porphyrin rings electron-withdrawing groups, such as halogen, nitro or cyano. These complexes are useful as catalysts for the oxidation of organic compounds, e.g. alkanes.

  4. Metal complexes of substituted Gable porphyrins as oxidation catalysts

    DOEpatents

    Lyons, James E.; Ellis, Jr., Paul E.; Wagner, Richard W.

    1996-01-01

    Transition metal complexes of Gable porphyrins having two porphyrin rings connected through a linking group, and having on the porphyrin rings electron-withdrawing groups, such as halogen, nitro or cyano. These complexes are useful as catalysts for the oxidation of organic compounds, e.g. alkanes.

  5. A new metalation complex for organic synthesis and polymerization reactions

    NASA Technical Reports Server (NTRS)

    Hirshfield, S. M.

    1971-01-01

    Organometallic complex of N,N,N',N' tetramethyl ethylene diamine /TMEDA/ and lithium acts as metalation intermediate for controlled systhesis of aromatic organic compounds and polymer formation. Complex of TMEDA and lithium aids in preparation of various organic lithium compounds.

  6. An Experiment on Isomerism in Metal-Amino Acid Complexes.

    ERIC Educational Resources Information Center

    Harrison, R. Graeme; Nolan, Kevin B.

    1982-01-01

    Background information, laboratory procedures, and discussion of results are provided for syntheses of cobalt (III) complexes, I-III, illustrating three possible bonding modes of glycine to a metal ion (the complex cations II and III being linkage/geometric isomers). Includes spectrophotometric and potentiometric methods to distinguish among the…

  7. Complexed metals in hazardous waste: Limitations of conventional chemical oxidation

    SciTech Connect

    Diel, B.N.; Kuchynka, D.J.; Borchert, J.

    1994-12-31

    In the management of hazardous waste, more is known regarding the treatment of metals than about the fixation, destruction and/or immobilization of any other hazardous constituent group. Metals are the only hazardous constituents which cannot be destroyed, and so must be converted to their least soluble and/or reactive form to prevent reentry into the environment. The occurrence of complexed metals, e.g., metallocyanides, and/or chelated metals, e.g., M{center_dot}EDTA in hazardous waste streams presents formidable challenges to conventional waste treatment practices. This paper presents the results of extensive research into the destruction (chemical oxidation) of metallocyanides and metal-chelates, defines the utility and limitations of conventional chemical oxidation approaches, illustrates some of the waste management difficulties presented by such species, and presents preliminary data on the UV/H{sub 2}O{sub 2} photodecomposition of chelated metals.

  8. A Triaxial Failure Diagram to predict the forming limit of 3D sheet metal parts subjected to multiaxial stresses

    NASA Astrophysics Data System (ADS)

    Rastellini, F.; Socorro, G.; Forgas, A.; Onate, E.

    2016-08-01

    Accurate prediction of failure and forming limits is essential when modelling sheet metal forming processes. Since traditional Forming Limit Curves (FLCs) are not valid for materials subjected to triaxial loading, a new failure criterion is proposed in this paper based on the stress triaxility and the effective plastic strain accumulated during the history of material loading. Formability zones are identified inside the proposed Triaxial Failure Diagram (TFD). FLCs may be mapped into the TFD defining a new Triaxial Failure Curve, or it can be defined by triaxial failure experiments. Several TFD examples are validated and constrasted showing acceptable accuracy in the numerical prediction of forming failure/limit of 3D thick sheet parts.

  9. Low-Molecular-Mass Metal Complexes in the Mouse Brain

    PubMed Central

    McCormick, Sean P.; Chakrabarti, Mrinmoy; Cockrell, Allison L.; Park, Jinkyu; Lindahl, Lora S.; Lindahl, Paul A.

    2013-01-01

    The presence of labile low-molecular-mass (LMM, defined as < 10 kDa) metal complexes in cells and super-cellular structures such as the brain has been inferred from chelation studies, but direct evidence is lacking. To evaluate the presence of LMM metal complexes in the brain, supernatant fractions of fresh mouse brain homogenates were passed through a 10 kDa cutoff membrane and subjected to size-exclusion liquid chromatography under anaerobic refrigerated conditions. Fractions were monitored for Mn, Fe, Co, Cu, Zn, Mo, S and P using an on-line ICP-MS. At least 30 different LMM metal complexes were detected along with numerous P- and S- containing species. Reproducibility was assessed by performing the experiment 13 times, using different buffers, and by examining whether complexes changed with time. Eleven Co, 2 Cu, 5 Mn, 4 Mo, 3 Fe and 2 Zn complexes with molecular masses < 4 kDa were detected. One LMM Mo complex comigrated with the molybdopterin cofactor. Most Cu and Zn complexes appeared to be protein-bound with masses ranging from 4 – 20 kDa. Co was the only metal for which the “free” or aqueous complex was reproducibly observed. Aqueous Co may be sufficiently stable in this environment due to its relatively slow water-exchange kinetics. Attempts were made to assign some of these complexes, but further efforts will be required to identify them unambiguously and to determine their functions. This is among the first studies to detect low-molecular-mass transition metal complexes in the mouse brain using LC-ICP-MS. PMID:23443205

  10. Occupational exposure to dust and lung disease among sheet metal workers.

    PubMed Central

    Hunting, K L; Welch, L S

    1993-01-01

    A previous large medical survey of active and retired sheet metal workers with 20 or more years in the trade indicated an unexpectedly high prevalence of obstructive pulmonary disease among both smokers and non-smokers. This study utilised interviews with a cross section of the previously surveyed group to explore occupational risk factors for lung disease. Four hundred and seven workers were selected from the previously surveyed group on the basis of their potential for exposure to fibreglass and asbestos. Selection was independent of health state, and excluded welders. A detailed history of occupational exposure was obtained by telephone interview for 333 of these workers. Exposure data were analysed in relation to previously collected data on chronic bronchitis, obstructive lung disease, and personal characteristics. Assessment of the effects of exposure to fibreglass as distinct from the effects of exposure to asbestos has been difficult in previous studies of construction workers. The experienced workers studied here have performed a diversity of jobs involving exposure to many different types of materials, and this enabled exposure to each dust to be evaluated separately. The risk of chronic bronchitis increased sharply by pack-years of cigarettes smoked; current smokers had a double risk compared with those who had never smoked or had stopped smoking. The occurrence of chronic bronchitis also increased with increasing duration of exposure to asbestos. Workers with a history of high intensity exposure to fibreglass had a more than doubled risk of chronic bronchitis. Obstructive lung disease, defined by results of pulmonary function tests at the medical survey, was also related to both smoking and occupational risk factors. Number of pack years smoked was the strongest predictor of obstructive lung disease. Duration of direct and indirect exposure to welding fume was also a positive predictor of obstructive lung disease. Duration of exposure to asbestos was

  11. Thermo Physics Facilities Branch Brochure ARC Jet Complex Fact Sheets, Hypervelocity Free-Flight Aerodynamic Facility Fact Sheets, Ames Vertical Gun Range Fact Sheets

    NASA Technical Reports Server (NTRS)

    Fretter, E. F. (Editor); Kuhns, Jay (Editor); Nuez, Jay (Editor)

    2003-01-01

    The Ames Arc Jet Complex has a rich heritage of over 40 years in Thermal Protection System (TPS) development for every NASA Space Transportation and Planetary program, including Apollo, Space Shuttle, Viking, Pioneer-Venus, Galileo, Mars Pathfinder,Stardust, NASP,X-33,X-34,SHARP-B1 and B2,X-37 and Mars Exploration Rovers. With this early TPS history came a long heritage in the development of the arc jet facilities. These are used to simulate the aerodynamic heating that occurs on the nose cap, wing leading edges and on other areas of the spacecraft requiring thermal protection. TPS samples have been run in the arc jets from a few minutes to over an hour,from one exposure to multiple exposures of the same sample, in order t o understand the TPS materials response to a hot gas flow environment (representative of real hyperthermal environments experienced in flight). The Ames Arc l e t Complex is a key enabler for customers involved in the three major areas of TPS development: selection, validation, and qualification. The arc jet data are critical for validating TPS thermal models, heat shield designs and repairs, and ultimately for flight qualification.

  12. Preparation of nanoporous metal foam from high nitrogen transition metal complexes

    DOEpatents

    Tappan, Bryce C.; Huynh, My Hang V.; Hiskey, Michael A.; Son, Steven F.; Oschwald, David M.; Chavez, David E.; Naud, Darren L.

    2006-11-28

    Nanoporous metal foams are prepared by ignition of high nitrogen transition metal complexes. The ammonium salts of iron(III) tris[bi(tetrazolato)-amine], cobalt(III) tris(bi(tetrazolato)amine), and high nitrogen compounds of copper and silver were prepared as loose powders, pressed into pellets and wafers, and ignited under an inert atmosphere to form nanoporous metal foam monoliths having very high surface area and very low density.

  13. The photochemistry of transition metal complexes using density functional theory.

    PubMed

    Garino, Claudio; Salassa, Luca

    2013-07-28

    The use of density functional theory (DFT) and time-dependent DFT (TD-DFT) to study the photochemistry of metal complexes is becoming increasingly important among chemists. Computational methods provide unique information on the electronic nature of excited states and their atomic structure, integrating spectroscopy observations on transient species and excited-state dynamics. In this contribution, we present an overview on photochemically active transition metal complexes investigated by DFT. In particular, we discuss a representative range of systems studied up to now, which include CO- and NO-releasing inorganic and organometallic complexes, haem and haem-like complexes dissociating small diatomic molecules, photoactive anti-cancer Pt and Ru complexes, Ru polypyridyls and diphosphino Pt derivatives.

  14. Metal Complexes of EDTA: An Exercise in Data Interpretation

    NASA Astrophysics Data System (ADS)

    Mitchell, Philip C. H.

    1997-10-01

    Stability constants of metal complexes of edta with main group and transition metals are correlated with properties of the elements and cations (ion charge, atomic and ionic radii, ionization energies and electronegativities) and interpreted with an ionic bonding model including a covalent contribution. Enthalpy and entropy contributions are discussed. It is shown how chemists recognize patterns in data with the help of a general theory and so develop a model.

  15. Positronium formation in solid transition metal losartanates complexes

    NASA Astrophysics Data System (ADS)

    de Oliveira, F. C.; Denadai, A. M. L.; Fulgêncio, F.; da Silva, J. G.; Windmöller, D.; Marques-Netto, A.; Machado, J. C.; Magalhães, W. F.

    2013-10-01

    In this Letter, positron annihilation lifetime (PALS) measurements were performed in transition metal losartanates complexes, MT(Los)2, and in potassium losartanate, KLos, in order to built up insights about the positronium formation mechanism in molecular environment. A correlation was obtained between formation probability, I3, and the covalence of complexes, evaluated by molar electrical conductivity in dimethylformamide (DMF). Furthermore, some metallic ion properties, such as reduction potential and pauling electronegativity, were also correlated with I3. These results were analyzed in terms of the spur model and of the recently proposed mechanism, named cybotatic correlated system kinetic mechanism (CCSKM), which involves molecular excited states in positronium formation.

  16. Luminescent molecular rods - transition-metal alkynyl complexes.

    PubMed

    Yam, Vivian Wing-Wah; Wong, Keith Man-Chung

    2005-01-01

    A number of transition-metal complexes have been reported to exhibit rich luminescence, usually originating from phosphorescence. Such luminescence properties of the triplet excited state with a large Stoke's shift, long lifetime, high luminescence quantum yield as well as lower excitation energy, are envisaged to serve as an ideal candidate in the area of potential applications for chemosensors, dye-sensitized solar cells, flat panel displays, optics, new materials and biological sciences. Organic alkynes (poly-ynes), with extended or conjugatedπ-systems and rigid structure with linear geometry, have become a significant research area due to their novel electronic and physical properties and their potential applications in nanotechnology. Owing to the presence of unsaturated sp-hybridized carbon atoms, the alkynyl unit can serve as a versatile building block in the construction of alkynyl transition-metal complexes, not only throughσ-bonding but also viaπ-bonding interactions. By incorporation of linear alkynyl groups into luminescent transition-metal complexes, the alkynyl moiety with goodσ-donor,π-donor andπ-acceptor abilities is envisaged to tune or perturb the emission behaviors, including emission energy (color), intensity and lifetime by its role as an auxiliary ligand as well as to govern the emission origin from its direct involvement. This review summarizes recent efforts on the synthesis of luminescent rod-like alkynyl complexes with different classes of transition metals and details the effects of the introduction of alkynyl groups on the luminescence properties of the complexes.

  17. Dinuclear transition metal complexes in carbon nanostructured materials synthesis

    NASA Astrophysics Data System (ADS)

    Ayuso, J. I.; Hernández, E.; Delgado, E.

    2013-06-01

    Carbon nanomaterials (CNMs) were prepared with two similar techniques using organometallic complexes as catalysts precursors. Chemical vapour deposition (CVD) and pyrolysis with chlorine gas approaches were employed in order to explore the effect of dinuclear transition metal compounds [Fe2(CO)6(μ-S2C6H2X2), (X=OH, Cl)] in synthesis of CNMs. Our to-date results have shown these complexes generate different carbonaceous materials when they are used in bulk, it was also observed that their performances in synthesis differ even though these compounds are analogous. With X=OH complex used in CVD process, metal nanoparticles of ca. 20-50 nm in size and embedded in carbon matrix were obtained. X=C1 complex has been used in pyrolysis experiments and showed an entire volatilisation or no reaction, depending on selected temperature. Furthermore, obtaining of a new tetranuclear iron cluster is presented in this work.

  18. Effect of metal nanoparticles decoration on electron field emission property of graphene sheets.

    PubMed

    Baby, Tessy Theres; Ramaprabhu, Sundara

    2011-10-05

    The electron field emission from metal nanoparticle decorated hydrogen exfoliated graphene (metal/HEG) occurs at low turn on and threshold fields due to its low work function and high field enhancement factor.

  19. A Microsample Tensile Test Application: Local Strength of Impact Welds Between Sheet Metals

    NASA Astrophysics Data System (ADS)

    Benzing, J. T.; He, M.; Vivek, A.; Taber, G. A.; Mills, M. J.; Daehn, G. S.

    2017-01-01

    Microsample tensile testing was conducted to evaluate the quality of impact welds created by vaporizing foil actuator welding. Tensile test samples with a gauge length of 0.6 mm were electro-discharge machined out of welds created between 1-mm-thick aluminum alloy type 6061 (AA6061) sheets and 6-mm-thick copper (Cu110) plates. Aluminum sheets were used as flyers, while copper plates acted as targets. Flyer sheets in T6 as well as T4 temper conditions were utilized to create welds. Some of the welds made with T4 temper flyers were heat treated to a T6 temper. It was found that the welds made with T4 temper flyers were slightly stronger (max. of 270 MPa) than those produced with T6 temper flyers. Generally, failure propagated in a brittle manner across the weld interface; however, elemental mapping reveals material transfer on either member of the welded system. This work proves the feasibility to apply microsample tensile testing to assess impact welding, even when conducted with flyer sheets of 1 mm or less, and provides insight that is complementary to other test methods.

  20. A Microsample Tensile Test Application: Local Strength of Impact Welds Between Sheet Metals

    NASA Astrophysics Data System (ADS)

    Benzing, J. T.; He, M.; Vivek, A.; Taber, G. A.; Mills, M. J.; Daehn, G. S.

    2017-03-01

    Microsample tensile testing was conducted to evaluate the quality of impact welds created by vaporizing foil actuator welding. Tensile test samples with a gauge length of 0.6 mm were electro-discharge machined out of welds created between 1-mm-thick aluminum alloy type 6061 (AA6061) sheets and 6-mm-thick copper (Cu110) plates. Aluminum sheets were used as flyers, while copper plates acted as targets. Flyer sheets in T6 as well as T4 temper conditions were utilized to create welds. Some of the welds made with T4 temper flyers were heat treated to a T6 temper. It was found that the welds made with T4 temper flyers were slightly stronger (max. of 270 MPa) than those produced with T6 temper flyers. Generally, failure propagated in a brittle manner across the weld interface; however, elemental mapping reveals material transfer on either member of the welded system. This work proves the feasibility to apply microsample tensile testing to assess impact welding, even when conducted with flyer sheets of 1 mm or less, and provides insight that is complementary to other test methods.

  1. Sheet resistance characterization of locally anisotropic transparent conductive films made of aligned metal-enriched single-walled carbon nanotubes.

    PubMed

    Kang, Hosung; Kim, Duckjong; Baik, Seunghyun

    2014-09-21

    One-dimensional conductive fillers such as single-walled carbon nanotubes (SWNTs) can be aggregated and aligned during transparent conductive film (TCF) formation by the vacuum filtration method. The potential error of analysing the average sheet resistance of these anisotropic films, using the four-point probe in-line method and the conversion formula developed assuming uniform isotropic material properties, was systematically investigated by finite element analysis and experiments. The finite element analysis of anisotropic stripe-patterned TCFs with alternating low (ρ1) and high (ρ2) resistivities revealed that the estimated average sheet resistance approached ρ1/t when the probes were parallel to the aligned nanotubes. The thickness of the film is t. It was more close to ρ2/t when the probes were perpendicular to the aligned tubes. Indeed, TCFs fabricated by the vacuum filtration method using metal-enriched SWNTs exhibited highly anisotropic local regions where tubes were aggregated and aligned. The local sheet resistances of randomly oriented, aligned, and perpendicular tube regions of the TCF at a transmittance of 89.9% were 5000, 2.4, and 12 300 Ω □(-1), respectively. Resistivities of the aggregated and aligned tube region (ρ1 = 1.2 × 10(-5) Ω cm) and the region between tubes (ρ2 = 6.2 × 10(-2) Ω cm) could be approximated with the aid of finite element analysis. This work demonstrates the potential error of characterizing the average sheet resistance of anisotropic TCFs using the four-point probe in-line method since surprisingly high or low values could be obtained depending on the measurement angle. On the other hand, a better control of aggregation and alignment of nanotubes would realize TCFs with a very small anisotropic resistivity and a high transparency.

  2. In-situ stress analysis with X-Ray diffraction for yield locus characterization of sheet metals

    SciTech Connect

    Güner, A.; Tekkaya, A. E.; Zillmann, B.; Lampke, T.

    2013-12-16

    A main problem in the field of sheet metal characterization is the inhomogeneous plastic deformation in the gauge regions of specimens which causes the analytically calculated stresses to differ from the sought state of stress acting in the middle of the gauge region. To overcome this problem, application of X-Ray diffraction is analyzed. For that purpose a mobile X-ray diffractometer and an optical strain measurement system are mounted on a universal tensile testing machine. This enables the recording of the whole strain and stress history of a material point. The method is applied to uniaxial tension tests, plane strain tension tests and shear tests to characterize the interstitial free steel alloy DC06. The applicability of the concepts of stress factors is verified by uniaxial tension tests. The experimentally obtained values are compared with the theoretical values calculated with crystal elasticity models utilizing the orientation distribution functions (ODF). The relaxation problem is addressed which shows itself as drops in the stress values with the strain kept at a constant level. This drop is analyzed with elasto-viscoplastic material models to correct the measured stresses. Results show that the XRD is applicable to measure the stresses in sheet metals with preferred orientation. The obtained yield locus is expressed with the Yld2000–2D material model and an industry oriented workpiece is analyzed numerically. The comparison of the strain distribution on the workpiece verifies the identified material parameters.

  3. Anticancer Activity of Metal Complexes: Involvement of Redox Processes

    PubMed Central

    Jungwirth, Ute; Kowol, Christian R.; Keppler, Bernhard K.; Hartinger, Christian G.; Berger, Walter; Heffeter, Petra

    2012-01-01

    Cells require tight regulation of the intracellular redox balance and consequently of reactive oxygen species for proper redox signaling and maintenance of metal (e.g., of iron and copper) homeostasis. In several diseases, including cancer, this balance is disturbed. Therefore, anticancer drugs targeting the redox systems, for example, glutathione and thioredoxin, have entered focus of interest. Anticancer metal complexes (platinum, gold, arsenic, ruthenium, rhodium, copper, vanadium, cobalt, manganese, gadolinium, and molybdenum) have been shown to strongly interact with or even disturb cellular redox homeostasis. In this context, especially the hypothesis of “activation by reduction” as well as the “hard and soft acids and bases” theory with respect to coordination of metal ions to cellular ligands represent important concepts to understand the molecular modes of action of anticancer metal drugs. The aim of this review is to highlight specific interactions of metal-based anticancer drugs with the cellular redox homeostasis and to explain this behavior by considering chemical properties of the respective anticancer metal complexes currently either in (pre)clinical development or in daily clinical routine in oncology. PMID:21275772

  4. First-principles studies of BN sheets with absorbed transition metal single atoms or dimers: stabilities, electronic structures, and magnetic properties.

    PubMed

    Ma, Dongwei; Lu, Zhansheng; Ju, Weiwei; Tang, Yanan

    2012-04-11

    BN sheets with absorbed transition metal (TM) single atoms, including Fe, Co, and Ni, and their dimers have been investigated by using a first-principles method within the generalized gradient approximation. All of the TM atoms studied are found to be chemically adsorbed on BN sheets. Upon adsorption, the binding energies of the Fe and Co single atoms are modest and almost independent of the adsorption sites, indicating the high mobility of the adatoms and isolated particles to be easily formed on the surface. However, Ni atoms are found to bind tightly to BN sheets and may adopt a layer-by-layer growth mode. The Fe, Co, and Ni dimers tend to lie (nearly) perpendicular to the BN plane. Due to the wide band gap of the pure BN sheet, the electronic structures of the BN sheets with TM adatoms are determined primarily by the distribution of TM electronic states around the Fermi level. Very interesting spin gapless semiconductors or half-metals can be obtained in the studied systems. The magnetism of the TM atoms is preserved well on the BN sheet, very close to that of the corresponding free atoms and often weakly dependent on the adsorption sites. The present results indicate that BN sheets with adsorbed TM atoms have potential applications in fields such as spintronics and magnetic data storage due to the special spin-polarized electronic structures and magnetic properties they possess.

  5. Computer simulation of supramolecular assembly by metal-ligand complexation

    NASA Astrophysics Data System (ADS)

    Wang, Shihu; Chen, Chun-Chung; Dormidontova, Elena E.

    2006-03-01

    Monte Carlo simulations were employed to study the supramolecular assembly of oligomers end-functionalized by ligands capable of complexation with metal ions. The properties of these metallo-supramolecular polymers strongly depend on the oligomer concentration, strength of complexation, and metal-to- ligand ratio. At high oligomer concentration the average molecular weight exhibits a maximum near the stoichiometric composition and decreases for higher or lower metal content. On the other hand, at low oligomer concentration the molecular weight shows a local minimum around the stoichiometric composition. This unusual behavior is attributed to the larger population of small rings around the stoichiometric composition, which make up a significant fraction of the overall molecular weight at low oligomer concentration. This effect is especially pronounced at low temperature, where the fraction of rings is higher. The fraction of chains and rings for different concentrations, temperatures and oligomer lengths were calculated and compared with experimental data.

  6. Rare earth metal oxazoline complexes in asymmetric catalysis.

    PubMed

    Ward, Benjamin D; Gade, Lutz H

    2012-11-07

    Polydentate oxazolines have been employed as highly effective stereodirecting ligands for asymmetric catalysis with metals from across most of the periodic table. Despite their highly versatile coordination chemistry, the use of these ligands tends to be polarised towards late transition metals; their use with early transition metals and the f-elements is significantly less developed. This current article aims to review the coordination chemistry and catalytic applications of Group 3 and lanthanide complexes supported by ligands possessing oxazoline moieties. Oxazoline-containing ligands were first employed in molecular lanthanide catalysis as early as 1997, yet there is still a significant void in the chemical literature in this respect. The ligands generally employed include bis(oxazolinyl)methane ("BOX"), 2,6-bis(oxazolinyl)pyridine ("pybox"), 1,1,1-tris(oxazolinyl)ethane ("trisox"), and others. The complexes are employed in a wide-range of catalytic applications, especially in Lewis acid catalysis, but also in the stereospecific polymerisation of olefins.

  7. Method for synthesizing metal bis(borano) hypophosphite complexes

    DOEpatents

    Cordaro, Joseph G.

    2013-06-18

    The present invention describes the synthesis of a family of metal bis(borano) hypophosphite complexes. One procedure described in detail is the syntheses of complexes beginning from phosphorus trichloride and sodium borohydride. Temperature, solvent, concentration, and atmosphere are all critical to ensure product formation. In the case of sodium bis(borano) hypophosphite, hydrogen gas was evolved upon heating at temperatures above 150.degree. C. Included in this family of materials are the salts of the alkali metals Li, Na and K, and those of the alkaline earth metals Mg and Ca. Hydrogen storage materials are possible. In particular the lithium salt, Li[PH.sub.2(BH.sub.3).sub.2], theoretically would contain nearly 12 wt % hydrogen. Analytical data for product characterization and thermal properties are given.

  8. Control of cerium oxidation state through metal complex secondary structures

    SciTech Connect

    Levin, Jessica R.; Dorfner, Walter L.; Carroll, Patrick J.; Schelter, Eric J.

    2015-08-11

    A series of alkali metal cerium diphenylhydrazido complexes, Mx(py)y[Ce(PhNNPh)4], M = Li, Na, and K, x = 4 (Li and Na) or 5 (K), and y = 4 (Li), 8 (Na), or 7 (K), were synthesized to probe how a secondary coordination sphere would modulate electronic structures at a cerium cation. The resulting electronic structures of the heterobimetallic cerium diphenylhydrazido complexes were found to be strongly dependent on the identity of the alkali metal cations. When M = Li+ or Na+, the cerium(III) starting material was oxidized with concomitant reduction of 1,2-diphenylhydrazine to aniline. Reduction of 1,2-diphenylhydrazine was not observed when M = K+, and the complex remained in the cerium(III) oxidation state. Oxidation of the cerium(III) diphenylhydrazido complex to the Ce(IV) diphenylhydrazido one was achieved through a simple cation exchange reaction of the alkali metals. As a result, UV-Vis spectroscopy, FTIR spectroscopy, electrochemistry, magnetic susceptibility, and DFT studies were used to probe the oxidation state and the electronic changes that occurred at the metal centre.

  9. Control of cerium oxidation state through metal complex secondary structures

    DOE PAGES

    Levin, Jessica R.; Dorfner, Walter L.; Carroll, Patrick J.; ...

    2015-08-11

    A series of alkali metal cerium diphenylhydrazido complexes, Mx(py)y[Ce(PhNNPh)4], M = Li, Na, and K, x = 4 (Li and Na) or 5 (K), and y = 4 (Li), 8 (Na), or 7 (K), were synthesized to probe how a secondary coordination sphere would modulate electronic structures at a cerium cation. The resulting electronic structures of the heterobimetallic cerium diphenylhydrazido complexes were found to be strongly dependent on the identity of the alkali metal cations. When M = Li+ or Na+, the cerium(III) starting material was oxidized with concomitant reduction of 1,2-diphenylhydrazine to aniline. Reduction of 1,2-diphenylhydrazine was not observedmore » when M = K+, and the complex remained in the cerium(III) oxidation state. Oxidation of the cerium(III) diphenylhydrazido complex to the Ce(IV) diphenylhydrazido one was achieved through a simple cation exchange reaction of the alkali metals. As a result, UV-Vis spectroscopy, FTIR spectroscopy, electrochemistry, magnetic susceptibility, and DFT studies were used to probe the oxidation state and the electronic changes that occurred at the metal centre.« less

  10. Vibrational energy transfer dynamics in ruthenium polypyridine transition metal complexes.

    PubMed

    Fedoseeva, Marina; Delor, Milan; Parker, Simon C; Sazanovich, Igor V; Towrie, Michael; Parker, Anthony W; Weinstein, Julia A

    2015-01-21

    Understanding the dynamics of the initial stages of vibrational energy transfer in transition metal complexes is a challenging fundamental question which is also of crucial importance for many applications, such as improving the performance of solar devices or photocatalysis. The present study investigates vibrational energy transport in the ground and the electronic excited state of Ru(4,4'-(COOEt)2-2,2-bpy)2(NCS)2, a close relative of the efficient "N3" dye used in dye-sensitized solar cells. Using the emerging technique of ultrafast two-dimensional infrared spectroscopy, we show that, similarly to other transition-metal complexes, the central Ru heavy atom acts as a "bottleneck" making the energy transfer from small ligands with high energy vibrational stretching frequencies less favorable and thereby affecting the efficiency of vibrational energy flow in the complex. Comparison of the vibrational relaxation times in the electronic ground and excited state of Ru(4,4'-(COOEt)2-2,2-bpy)2(NCS)2 shows that it is dramatically faster in the latter. We propose to explain this observation by the intramolecular electrostatic interactions between the thiocyanate group and partially oxidised Ru metal center, which increase the degree of vibrational coupling between CN and Ru-N modes in the excited state thus reducing structural and thermodynamic barriers that slow down vibrational relaxation and energy transport in the electronic ground state. As a very similar behavior was earlier observed in another transition-metal complex, Re(4,4'-(COOEt)2-2,2'-bpy)(CO)3Cl, we suggest that this effect in vibrational energy dynamics might be common for transition-metal complexes with heavy central atoms.

  11. Battery with a microcorrugated, microthin sheet of highly porous corroded metal

    DOEpatents

    LaFollette, Rodney M.

    2005-09-27

    Microthin sheet technology is disclosed by which superior batteries are constructed which, among other things, accommodate the requirements for high load rapid discharge and recharge, mandated by electric vehicle criteria. The microthin sheet technology has process and article overtones and can be used to form thin electrodes used in batteries of various kinds and types, such as spirally-wound batteries, bipolar batteries, lead acid batteries silver/zinc batteries, and others. Superior high performance battery features include: (a) minimal ionic resistance; (b) minimal electronic resistance; (c) minimal polarization resistance to both charging and discharging; (d) improved current accessibility to active material of the electrodes; (e) a high surface area to volume ratio; (f) high electrode porosity (microporosity); (g) longer life cycle; (h) superior discharge/recharge characteristics; (i) higher capacities (A.multidot.hr); and (j) high specific capacitance.

  12. Surface Complexation Modelling in Metal-Mineral-Bacteria Systems

    NASA Astrophysics Data System (ADS)

    Johnson, K. J.; Fein, J. B.

    2002-12-01

    The reactive surfaces of bacteria and minerals can determine the fate, transport, and bioavailability of aqueous heavy metal cations. Geochemical models are instrumental in accurately accounting for the partitioning of the metals between mineral surfaces and bacteria cell walls. Previous research has shown that surface complexation modelling (SCM) is accurate in two-component systems (metal:mineral and metal:bacteria); however, the ability of SCMs to account for metal distribution in mixed metal-mineral-bacteria systems has not been tested. In this study, we measure aqueous Cd distributions in water-bacteria-mineral systems, and compare these observations with predicted distributions based on a surface complexation modelling approach. We measured Cd adsorption in 2- and 3-component batch adsorption experiments. In the 2-component experiments, we measured the extent of adsorption of 10 ppm aqueous Cd onto either a bacterial or hydrous ferric oxide sorbent. The metal:bacteria experiments contained 1 g/L (wet wt.) of B. subtilis, and were conducted as a function of pH; the metal:mineral experiments were conducted as a function of both pH and HFO content. Two types of 3-component Cd adsorption experiments were also conducted in which both mineral powder and bacteria were present as sorbents: 1) one in which the HFO was physically but not chemically isolated from the system using sealed dialysis tubing, and 2) others where the HFO, Cd and B. subtilis were all in physical contact. The dialysis tubing approach enabled the direct determination of the concentration of Cd on each sorbing surface, after separation and acidification of each sorbent. The experiments indicate that both bacteria and mineral surfaces can dominate adsorption in the system, depending on pH and bacteria:mineral ratio. The stability constants, determined using the data from the 2-component systems, along with those for other surface and aqueous species in the systems, were used with FITEQL to

  13. Transition metal complexes of an isatinic quinolyl hydrazone

    PubMed Central

    2011-01-01

    Background The importance of the isatinic quinolyl hydrazones arises from incorporating the quinoline ring with the indole ring in the same compound. Quinoline ring has therapeutic and biological activities. On the other hand, isatin (1H-indole-2,3-dione) and its derivatives exhibit a wide range of biological activities. Also, the indole ring occurs in Jasmine flowers and Orange blossoms. Recently, the physiological and biological activities of quinolyl hydrazones arise from their tendency to form metal chelates with transition metal ions. In this context, we have reported to isolate, characterize and study the biological activity of some transition metal complexes of an isatinic quinolyl hydrazone; 3-[2-(4-methyl quinolin-2-yl)hydrazono] indolin-2-one. Results Mono- and binuclear as well as dimeric chelates were obtained from the reaction of a new isatinic quinolyl hydrazone with Fe(III), Co(II), Ni(II), Cu(II), VO(II) and Pd(II) ions. The ligand showed a variety of modes of bonding viz. (NNO)2-, (NO)- and (NO) per each metal ion supporting its ambidentate and flexidentate characters. The mode of bonding and basicity of the ligand depend mainly on the type of the metal cation and its counter anion. All the obtained Pd(II)- complexes have the preferable square planar geometry (D4h- symmetry) and depend mainly on the mole ratio (M:L). Conclusion The effect of the type of the metal ion for the same anion (Cl-) is obvious from either structural diversity of the isolated complexes (Oh, Td and D4h) or the various modes of bonding. The isatinic hydrazone uses its lactim form in all complexes (Cl-) except complex 5 (SO42-) in which it uses its lactam form. The obtained Pd(II)- complexes (dimeric, mono- and binuclear) are affected by the mole ratio (M:L) and have the square planar (D4h) geometry. Also, the antimicrobial activity is highly influenced by the nature of the metal ion and the order for S. aureus bacteria is as follows: Nickel(II) > Vanadyl(II) > Cobalt

  14. Numerical Modeling of Magnesium Alloy Sheet Metal Forming at Elevated Temperature

    SciTech Connect

    Lee, Myeong-Han; Oh, Soo-Ik; Kim, Heon-Young; Kim, Hyung-Jong; Choi, Yi-Chun

    2007-05-17

    The development of light-weight vehicle is in great demand for enhancement of fuel efficiency and dynamic performance. The vehicle weight can be reduced effectively by using lightweight materials such as magnesium alloys. However, the use of magnesium alloys in sheet forming processes is still limited because of their low formability at room temperature and the lack of understanding of the forming process of magnesium alloys at elevated temperatures. In this study, uniaxial tensile tests of the magnesium alloy AZ31B-O at various temperatures were performed to evaluate the mechanical properties of this alloy relevant for forming of magnesium sheets. To construct a FLD (forming limit diagram), a forming limit test were conducted at temperature of 100 and 200 deg. C. For the evaluation of the effects of the punch temperature on the formability of a rectangular cup drawing with AZ31B-O, numerical modelling was conducted. The experiment results indicate that the stresses and possible strains of AZ31B-O sheets largely depend on the temperature. The stress decreases with temperature increase. Also, the strain increase with temperature increase. The numerical modelling results indicate that formability increases with the decrease in the punch temperature at the constant temperature of the die and holder.

  15. dc-Sheet resistance as sensitive monitoring tool of protein immobilization on thin metal films.

    PubMed

    Neff, H; Beeby, T; Lima, A M N; Borre, M; Thirstrup, C; Zong, W; de Almeida, L A L

    2006-03-15

    The suitability of high resolution, in situ dc-sheet resistance monitoring (SRM) as a simplified and reliable sensing technique towards detection and tracking of protein immobilization has been explored. Non-specific adsorption of bovine serum albumin (BSA) onto a very thin gold film, acting as the sensing resistor, has been employed as a model system. For comparison, the novel sensing method was combined with surface plasmon resonance (SPR) spectroscopy, using the same flow cell and sensing surface. Two different, well known adsorption states, involving a composite layer of irreversibly and reversibly bound BSA, were clearly resolved by both methods. Clearly structured, pronounced and fully reproducible film resistance modulations have been resolved in the associated SRM data. The transition from reversibly bound BSA to the diluted protein phase is associated with an unusually large decrease in the dc-sheet resistance. The observed resistance modulation magnitude for an adsorbed BSA monolayer corresponds to approximately 1%, and up to 100 mOmega at a 10 Omega sensing resistor. The sheet resistance of irreversibly bound BSA was determined to 0.24 kOmega/cm2, and the associated specific resistivity estimated to 1-2x10(4) Omega cm.

  16. Electron transfer and catalysis with high-valent metal-oxo complexes.

    PubMed

    Fukuzumi, Shunichi

    2015-04-21

    High-valent metal-oxo complexes are produced by reductive activation of dioxygen via reduction of metal complexes with reductants and dioxygen. Photoinduced electron transfer from substrates to metal complexes with dioxygen also leads to the generation of high-valent metal-oxo complexes that can oxygenate substrates. In such a case metal complexes act as a photocatalyst to oxygenate substrates with dioxygen. High-valent metal-oxo complexes are also produced by proton-coupled electron-transfer oxidation of metal complexes by one-electron oxidants with water, oxygenating substrates to regenerate metal complexes. In such a case metal complexes act as a catalyst for electron-transfer oxygenation of substrates by one-electron oxidants with water that acts as an oxygen source. The one-electron oxidants which can oxidize metal complexes can be replaced by much weaker oxidants by a combination of redox photocatalysts and metal complexes. Thus, photocatalytic oxygenation of substrates proceeds via photoinduced electron transfer from a photocatalyst to reductants followed by proton-coupled electron transfer oxidation of metal complexes with the oxidized photocatalyst to produce high-valent metal-oxo complexes that oxygenate substrates. Thermal and photoinduced electron-transfer catalytic reactions of high-valent metal-oxo complexes for oxygenation of substrates using water or dioxygen as an oxygen source are summarized in this perspective.

  17. Efficiently engineered cell sheet using a complex of polyethylenimine–alginate nanocomposites plus bone morphogenetic protein 2 gene to promote new bone formation

    PubMed Central

    Jin, Han; Zhang, Kai; Qiao, Chunyan; Yuan, Anliang; Li, Daowei; Zhao, Liang; Shi, Ce; Xu, Xiaowei; Ni, Shilei; Zheng, Changyu; Liu, Xiaohua; Yang, Bai; Sun, Hongchen

    2014-01-01

    Regeneration of large bone defects is a common clinical problem. Recently, stem cell sheet has been an emerging strategy in bone tissue engineering. To enhance the osteogenic potential of stem cell sheet, we fabricated bone morphogenetic protein 2 (BMP-2) gene-engineered cell sheet using a complex of polyethylenimine–alginate (PEI–al) nanocomposites plus human BMP-2 complementary(c)DNA plasmid, and studied its osteogenesis in vitro and in vivo. PEI–al nanocomposites carrying BMP-2 gene could efficiently transfect bone marrow mesenchymal stem cells. The cell sheet was made by culturing the cells in medium containing vitamin C for 10 days. Assays on the cell culture showed that the genetically engineered cells released the BMP-2 for at least 14 days. The expression of osteogenesis-related gene was increased, which demonstrated that released BMP-2 could effectively induce the cell sheet osteogenic differentiation in vitro. To further test the osteogenic potential of the cell sheet in vivo, enhanced green fluorescent protein or BMP-2-producing cell sheets were treated on the cranial bone defects. The results indicated that the BMP-2-producing cell sheet group was more efficient than other groups in promoting bone formation in the defect area. Our results suggested that PEI–al nanocomposites efficiently deliver the BMP-2 gene to bone marrow mesenchymal stem cells and that BMP-2 gene-engineered cell sheet is an effective way for promoting bone regeneration. PMID:24855355

  18. Metal Complexes for DNA-Mediated Charge Transport

    PubMed Central

    Barton, Jacqueline K.; Olmon, Eric D.; Sontz, Pamela A.

    2010-01-01

    In all organisms, oxidation threatens the integrity of the genome. DNA-mediated charge transport (CT) may play an important role in the generation and repair of this oxidative damage. In studies involving long-range CT from intercalating Ru and Rh complexes to 5′-GG-3′ sites, we have examined the efficiency of CT as a function of distance, temperature, and the electronic coupling of metal oxidants bound to the base stack. Most striking is the shallow distance dependence and the sensitivity of DNA CT to how the metal complexes are stacked in the helix. Experiments with cyclopropylamine-modified bases have revealed that charge occupation occurs at all sites along the bridge. Using Ir complexes, we have seen that the process of DNA-mediated reduction is very similar to that of DNA-mediated oxidation. Studies involving metalloproteins have, furthermore, shown that their redox activity is DNA-dependent and can be DNA-mediated. Long range DNA-mediated CT can facilitate the oxidation of DNA-bound base excision repair proteins to initiate a redox-active search for DNA lesions. DNA CT can also activate the transcription factor SoxR, triggering a cellular response to oxidative stress. Indeed, these studies show that within the cell, redox-active proteins may utilize the same chemistry as that of synthetic metal complexes in vitro, and these proteins may harness DNA-mediated CT to reduce damage to the genome and regulate cellular processes. PMID:21643528

  19. Green synthesis of multi metal- citrate complexes and their characterization

    NASA Astrophysics Data System (ADS)

    Raju, Usha; Warkar, Sudhir G.; Kumar, Anil

    2017-04-01

    Four new multi metal-citrate complexes have been synthesized through green synthetic pathways. Their synthesis by hydrothermal route in the present research is decorated with features such as, a simple one pot synthesis, cost effectiveness, easy to scale up for commercial production, efficient synthesis conditions like mild temperature and shorter duration which further rules out the possibility of forming byproducts which may cause damage to the environment and being environmental benign as it eliminates the use and recovery of harmful organic solvents such as N, N- dimethyl formamide and N, N- diethyl formamide, used by the researchers in the past during the synthesis of similar metal- organic framework complexes. All four complexes are well defined crystalline materials with polynuclear multi metal-citrate framework having cubic crystal structure as indicated by their Powder X-ray Diffraction patterns. These complexes have been characterized by Fourier Transform Infrared Spectroscopy, Scanning Electron Microscopy, Energy Dispersive X-ray Spectroscopy, Thermogravimetric analysis and Powder XRD techniques.

  20. Photoinduced energy transfer in transition metal complex oligomers

    SciTech Connect

    1997-06-01

    The work done over the past three years has been directed toward the preparation, characterization and photophysical examination of mono- and bimetallic diimine complexes. The work is part of a broader project directed toward the development of stable, efficient, light harvesting arrays of transition metal complex chromophores. One focus has been the synthesis of rigid bis-bidentate and bis-tridentate bridging ligands. The authors have managed to make the ligand bphb in multigram quantities from inexpensive starting materials. The synthetic approach used has allowed them to prepare a variety of other ligands which may have unique applications (vide infra). They have prepared, characterized and examined the photophysical behavior of Ru(II) and Re(I) complexes of the ligands. Energy donor/acceptor complexes of bphb have been prepared which exhibit nearly activationless energy transfer. Complexes of Ru(II) and Re(I) have also been prepared with other polyunsaturated ligands in which two different long lived (> 50 ns) excited states exist; results of luminescence and transient absorbance measurements suggest the two states are metal-to-ligand charge transfer and ligand localized {pi}{r_arrow}{pi}* triplets. Finally, the authors have developed methods to prepare polymetallic complexes which are covalently bound to various surfaces. The long term objective of this work is to make light harvesting arrays for the sensitization of large band gap semiconductors. Details of this work are provided in the body of the report.

  1. Photoinduced energy transfer in transition metal complex oligomers

    SciTech Connect

    1997-04-01

    The work we have done over the past three years has been directed toward the preparation, characterization and photophysical examination of mono- and bimetallic diimine complexes. The work is part of a broader project directed toward the development of stable, efficient, light harvesting arrays of transition metal complex chromophores. One focus has been the synthesis of rigid bis-bidentate and bis-tridentate bridging ligands. We have managed to make the ligand bphb in multigram quantities from inexpensive starting materials. The synthetic approach used has allowed us prepare a variety of other ligands which may have unique applications (vide infra). We have prepared, characterized and examined the photophysical behavior of Ru(II) and Re(I) complexes of the ligands. Energy donor/acceptor complexes of bphb have been prepared which exhibit nearly activationless energy transfer. Complexes of Ru(II) and Re(I) have also been prepared with other polyunsaturated ligands in which two different long lived ( > 50 ns) excited states exist; results of luminescence and transient absorbance measurements suggest the two states are metal-to-ligand charge transfer and ligand localized {pi}{r_arrow}{pi}* triplets. Finally, we have developed methods to prepare polymetallic complexes which are covalently bound to various surfaces. The long term objective of this work is to make light harvesting arrays for the sensitization of large band gap semiconductors. Details of this work are provided in the body of the report.

  2. Electric relaxation processes in chemodynamics of aqueous metal complexes: from simple ligands to soft nanoparticulate complexants.

    PubMed

    van Leeuwen, Herman P; Buffle, Jacques; Town, Raewyn M

    2012-01-10

    The chemodynamics of metal complexes with nanoparticulate complexants can differ significantly from that for simple ligands. The spatial confinement of charged sites and binding sites to the nanoparticulate body impacts on the time scales of various steps in the overall complex formation process. The greater the charge carried by the nanoparticle, the longer it takes to set up the counterion distribution equilibrium with the medium. A z+ metal ion (z > 1) in a 1:1 background electrolyte will accumulate in the counterionic atmosphere around negatively charged simple ions, as well as within/around the body of a soft nanoparticle with negative structural charge. The rate of accumulation is often governed by diffusion and proceeds until Boltzmann partition equilibrium between the charged entity and the ions in the medium is attained. The electrostatic accumulation proceeds simultaneously with outer-sphere and inner-sphere complex formation. The rate of the eventual inner-sphere complex formation is generally controlled by the rate constant of dehydration of the metal ion, k(w). For common transition metal ions with moderate to fast dehydration rates, e.g., Cu(2+), Pb(2+), and Cd(2+), it is shown that the ionic equilibration with the medium may be the slower step and thus rate-limiting in their overall complexation with nanoparticles.

  3. Selective transformations of cyclopentadienyl ligands of transition-metal and rare-earth metal complexes.

    PubMed

    Liu, Ruiting; Zhou, Xigeng

    2013-04-21

    Cyclopentadienyl and substituted cyclopentadienyl ligands are observed in a wide range of organometallic complexes. In addition to serving as ancillary ligands, these ligands have come into their own as intermediates in organometallic reactions, and shown many unique reaction modes involving ring C-H, C-C and C=C bond cleavages. This feature article summarizes the progressive development of cyclopentadienyl-based reactions of metallocene complexes of transition metals and rare-earth metals, with the aim of further developing the fundamental modes of reactivity of such systems together with their synthetic applications.

  4. Interplay of metal-allyl and metal-metal bonding in dimolybdenum allyl complexes

    SciTech Connect

    John, Kevin D; Martin, Richard L; Obrey, Steven J; Scott, Brian L

    2008-01-01

    Addition of PMe{sub 3} to Mo{sub 2}(allyl){sub 4} afforded Mo{sub 2}(allyl){sub 4}(PMe{sub 3}){sub 2}, in which two of the allyl groups adopt an unprecedented {mu}{sub 2{sup -}}{eta}{sup 1}, {eta}{sup 3} bonding mode; theoretical studies elucidate the role sof the {sigma}- and {pi}-donor ligands in the interplay of metal-allyl and metal-metal bonding.

  5. Permethrin-treated chaddars and top-sheets: appropriate technology for protection against malaria in Afghanistan and other complex emergencies.

    PubMed

    Rowland, M; Durrani, N; Hewitt, S; Mohammed, N; Bouma, M; Carneiro, I; Rozendaal, J; Schapira, A

    1999-01-01

    Insecticide-treated mosquito nets (ITN) provide excellent protection against malaria; however, they have a number of shortcomings that are particularly evident in politically unstable countries or countries at war: not everyone at risk can necessarily afford a net, nets may be difficult to obtain or import, nets may not be suitable for migrants or refugees sleeping under tents or plastic shelter. There is a need to develop cheaper, locally appropriate alternatives for the most impoverished and for victims of complex emergencies. Afghan women, in common with many Muslim peoples of Asia, wear a veil or wrap known as a chaddar to cover the head and upper body. This cloth doubles as a sheet at night, when they are used by both sexes. A randomized controlled trial was undertaken in which 10% of the families of an Afghan refugee camp (population 3950) in north-western Pakistan had their chaddars and top-sheets treated with permethrin insecticide at a dosage of 1 g/m2 while a further 10% had their chaddars treated with placebo formulation. Malaria episodes were recorded by passive case detection at the camp's health centre. From August to November the odds of having a falciparum or vivax malaria episode were reduced by 64% in children aged 0-10 years and by 38% in refugees aged < 20 years in the group using permethrin-treated chaddars and top-sheets. Incidence in refugees over 20 years of age was not significantly reduced. The cost of the permethrin treatment per person protected (US$0.17) was similar to that for treating bednets (and cost only 10-20% of the price of a new bednet). An entomological study simulating real-life conditions indicated that host-seeking mosquitoes were up to 70% less successful at feeding on men sleeping under treated chaddars and some were killed by the insecticide. Permethrin-treated top-sheets and blankets should provide appropriate and effective protection from malaria in complex emergencies. In Islamic and non-Islamic countries in Asia

  6. Inhomogeneous complexation of trace metals in water with organic nano-complexants

    NASA Astrophysics Data System (ADS)

    Dolgin, Bella; Bulatov, Valery; Hadar-Abuhatzira, Hodayah; Japarov, Julia; Schechter, Israel

    2011-12-01

    The complexation of heavy metals, such as Cd 2+ and Ni 2+, with organic complexants such as 1-(2-pyridylazo)-2-naphthol (PAN) and 1-(2-thiazolylazo)-2-naphthol (TAN) in water has been investigated. Under such conditions, both the reagents and the products form nano-particulates. These materials are important because their spectrum changes upon exposure to heavy metals and they may be used for design of new optical detectors. The kinetic schemes so far suggested for these complexation reactions are not valid for such experimental conditions, since they assume homogeneous behavior. We provide evidences to the inhomogeneous nature of these reactions. The complexation has been studied using TEM imaging, zeta-potentiometry, time-dependent particulate size analysis and time-dependent spectroscopy. Many of the experimental results are explained in terms of the nature of the nano-particulates of these two complexants. Several processes were identified, including crystal growing of the complexant, its reaction with metal ions in solution and on the surface area, chemical erosion of complexant crystallites and their decomposition, re-crystallization of the formed complexes and long term aggregation of both the complexant and the resulted complex. It was found that the needle-like nano-structures on the surface of the TAN particulates governs its reaction and particulate behavior. The known optimal complexation conditions, such as pH, and delay time are now understood in terms of the zeta-potential minima of the suspensions and in terms of the kinetic parameters. Also the interferences of some ions in the Ni-TAN complexation are now quantified and the kinetic data indicate the best delay time when the interfering effects are minimal.

  7. Interaction of PiB-derivative metal complexes with beta-amyloid peptides: selective recognition of the aggregated forms.

    PubMed

    Martins, André F; Dias, David M; Morfin, Jean-François; Lacerda, Sara; Laurents, Douglas V; Tóth, Éva; Geraldes, Carlos F G C

    2015-03-27

    Metal complexes are increasingly explored as imaging probes in amyloid peptide related pathologies. We report the first detailed study on the mechanism of interaction between a metal complex and both the monomer and the aggregated form of Aβ1-40 peptide. We have studied lanthanide(III) chelates of two PiB-derivative ligands (PiB=Pittsburgh compound B), L(1) and L(2), differing in the length of the spacer between the metal-complexing DO3A macrocycle (DO3A=1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid) and the peptide-recognition PiB moiety. Surface plasmon resonance (SPR) and saturation transfer difference (STD) NMR spectroscopy revealed that they both bind to aggregated Aβ1-40 (KD =67-160 μM), primarily through the benzothiazole unit. HSQC NMR spectroscopy on the (15) N-labeled, monomer Aβ1-40 peptide indicates nonsignificant interaction with monomeric Aβ. Time-dependent circular dichroism (CD), dynamic light scattering (DLS), and TEM investigations of the secondary structure and of the aggregation of Aβ1-40 in the presence of increasing amounts of the metal complexes provide coherent data showing that, despite their structural similarity, the two complexes affect Aβ fibril formation distinctly. Whereas GdL(1), at higher concentrations, stabilizes β-sheets, GdL(2) prevents aggregation by promoting α-helical structures. These results give insight into the behavior of amyloid-targeted metal complexes in general and contribute to a more rational design of metal-based diagnostic and therapeutic agents for amyloid- associated pathologies.

  8. Polynuclear transition metal complexes with thiocarbohydrazide and dithiocarbamates

    NASA Astrophysics Data System (ADS)

    Siddiqi, K. S.; Khan, Sadaf; Nami, Shahab A. A.; El-ajaily, M. M.

    2007-07-01

    Sn(tch) 2{MCl 2} 2 was prepared from the precursor Sn(tch) 2 and MCl 2. It was subsequently allowed to react with diethyldithiocarbamate which yielded the trinuclear complexes of the type Sn(tch) 2{M 2(dtc) 4}, where tch = thiocarbohydrazide, M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and dtc = diethyldithiocarbamate. They were characterized on the basis of microanalytical, thermal (TGA/DSC), spectral (IR, UV-vis, EPR, 1H NMR) studies, conductivity measurement and magnetic moment data. On the basis of spectral data a tetrahedral geometry has been proposed for the halide complexes, Sn(tch) 2{MCl 2} 2 except for Cu(II) which exhibits a square planar coordination although the transition metal ion in Sn(tch) 2{M 2(dtc) 4} achieves an octahedral geometry where the dithiocarbamato moiety acts as a symmetrical bidentate ligand. The bidentate nature has been established by the appearance of a sharp single ν(C-S) around 1000 cm -1. A downfield shift observed in NH a and NH b protons on moving from Sn(tch) 2 to Sn(tch) 2{MCl 2} 2 is due to the drift of electrons toward metal atoms. A two-step pyrolysis has been observed in the Sn(tch) 2{MCl 2} 2 complexes while their dithiocarbamato derivatives exhibit a three-stage degradation pattern. Finally, the in vitro antibacterial activity of Sn(tch) 2{M 2(dtc) 4} and the mononuclear Sn(tch) 2 has been carried out on bacterial strains Escherichia coli and Salmonella typhi. The compounds were found to be active against the test organisms. The activity of the complexes is enhanced with increasing concentration. The maximum activity in both the strains was achieved by cobalt(II) dithiocarbamate complex. Minimum activity was found for Sn(tch) 2 which generally increases with the introduction of transition metal ion in the complex.

  9. Blue metal complex pigments involved in blue flower color

    PubMed Central

    Takeda, Kosaku

    2006-01-01

    The blue pigment of cornflower, protocyanin, has been investigated for a long time, but its precise structure was not entirely explained until recently. The molecular structure of the pigment was recently shown to be a metal complex of six molecules each of anthocyanin and flavone glycoside, with one ferric iron, one magnesium and two calcium ions by X-ray crystallographic analysis. The studies provided the answer to the question posed in the early part of the last century, “why is the cornflower blue and rose red when both flowers contain the same anthocyanin?” This work was achieved on the basis of the results of long years of the studies made by many researchers. In this review, the author focuses on the investigations of the blue metal complex pigments involved in the bluing of flowers, commelinin from Commelina commusis, protocyanin from Centaurea cyanus, protodelphin from Salvia patens and hydrangea blue pigment. PMID:25792777

  10. Blue metal complex pigments involved in blue flower color.

    PubMed

    Takeda, Kosaku

    2006-05-01

    The blue pigment of cornflower, protocyanin, has been investigated for a long time, but its precise structure was not entirely explained until recently. The molecular structure of the pigment was recently shown to be a metal complex of six molecules each of anthocyanin and flavone glycoside, with one ferric iron, one magnesium and two calcium ions by X-ray crystallographic analysis. The studies provided the answer to the question posed in the early part of the last century, "why is the cornflower blue and rose red when both flowers contain the same anthocyanin?" This work was achieved on the basis of the results of long years of the studies made by many researchers. In this review, the author focuses on the investigations of the blue metal complex pigments involved in the bluing of flowers, commelinin from Commelina commusis, protocyanin from Centaurea cyanus, protodelphin from Salvia patens and hydrangea blue pigment.

  11. Dynamic inclusion complexes of metal nanoparticles inside nanocups.

    PubMed

    Alarcón-Correa, Mariana; Lee, Tung-Chun; Fischer, Peer

    2015-06-01

    Host-guest inclusion complexes are abundant in molecular systems and of fundamental importance in living organisms. Realizing a colloidal analogue of a molecular dynamic inclusion complex is challenging because inorganic nanoparticles (NPs) with a well-defined cavity and portal are difficult to synthesize in high yield and with good structural fidelity. Herein, a generic strategy towards the fabrication of dynamic 1:1 inclusion complexes of metal nanoparticles inside oxide nanocups with high yield (>70%) and regiospecificity (>90%) by means of a reactive double Janus nanoparticle intermediate is reported. Experimental evidence confirms that the inclusion complexes are formed by a kinetically controlled mechanism involving a delicate interplay between bipolar galvanic corrosion and alloying-dealloying oxidation. Release of the NP guest from the nanocups can be efficiently triggered by an external stimulus.

  12. Rigid-plastic and elastic-plastic finite element analysis on the clinching joint process of thin metal sheets

    NASA Astrophysics Data System (ADS)

    Jayasekara, Vishara; Min, Kyung Ho; Noh, Jeong Hoon; Kim, Min Tae; Seo, Jeong Min; Lee, Ho Yong; Hwang, Beong Bok

    2010-04-01

    This article describes the joining of thin metal sheets by a single stroke clinching process. Elastic-plastic and rigid-plastic finite element analysis were applied by employing Coulomb friction and constant shear friction in order to investigate the behavior of the clinch joint formation process. Four process variables, such as die diameter, die depth, groove width, and groove corner radius were selected to investigate the parametric effect on the clinch joint. The strength of clinch joints were evaluated by examining the separation strengths, such as peel strength and tensile shear strength, respectively. A failure diagram was constructed that summarizes the analysis results. The simulation results showed that die diameter and depth were the most decisive parameters for controlling the quality of the clinch joint, while the bottom's thickness was the most important evaluation parameter to determine the separation strengths.

  13. On the use of solid-shell elements for thin structures: Application to impact and sheet metal forming simulations

    NASA Astrophysics Data System (ADS)

    Wang, Peng; Chalal, Hocine; Abed-Meraim, Farid

    2016-10-01

    A family of linear and quadratic assumed-strain based solid-shell elements (SHB) is presented in this paper to simulate 3D thin structural problems including both quasi-static and dynamic analyses. The SHB solid-shell elements are based on a three-dimensional formulation, with only displacements as degrees of freedom, and a reduced integration technique with an arbitrary number of integration points along the thickness direction, which enables them to model 3D thin structures with only one layer of elements through the thickness. All SHB elements have been successfully implemented into ABAQUS dynamic/explicit and static/implicit codes. Several static and dynamic benchmark tests as well as sheet metal forming process simulations, involving large strain, material nonlinearity and contact, have been conducted to assess the performance of the SHB elements.

  14. A simple, general route to 2-pyridylidene transition metal complexes.

    PubMed

    Roselló-Merino, Marta; Díez, Josefina; Conejero, Salvador

    2010-12-28

    Pyridinium 2-carboxylates decompose thermally in the presence of a variety of late transition metal precursors to yield the corresponding 2-pyridylidene-like complexes. The mild reaction conditions and structural diversity that can be generated in the heterocyclic ring make this method an attractive alternative for the synthesis of 2-pyridylidene complexes. IR spectra of the Ir(i) carbonyl compounds [IrCl(NHC)(CO)(2)] indicate that these N-heterocyclic carbene ligands are among the strongest σ-electron donors.

  15. mer and fac isomerism in tris chelate diimine metal complexes.

    PubMed

    Dabb, Serin L; Fletcher, Nicholas C

    2015-03-14

    In this perspective, we highlight the issue of meridional (mer) and facial (fac) orientation of asymmetrical diimines in tris-chelate transition metal complexes. Diimine ligands have long been the workhorse of coordination chemistry, and whilst there are now good strategies to isolate materials where the inherent metal centered chirality is under almost complete control, and systematic methodologies to isolate heteroleptic complexes, the conceptually simple geometrical isomerism has not been widely investigated. In systems where the two donor atoms are significantly different in terms of the σ-donor and π-accepting ability, the fac isomer is likely to be the thermodynamic product. For the diimine complexes with two trigonal planar nitrogen atoms there is much more subtlety to the system, and external factors such as the solvent, lattice packing and the various steric considerations play a delicate role in determining the observed and isolable product. In this article we discuss the possibilities to control the isomeric ratio in labile systems, consider the opportunities to separate inert complexes and discuss the observed differences in their spectroscopic properties. Finally we report on the ligand orientation in supramolecular systems where facial coordination leads to simple regular structures such as helicates and tetrahedra, but the ability of the ligand system to adopt a mer orientation enables self-assembled structures of considerable beauty and complexity.

  16. Asymmetric Schiff bases derived from diaminomaleonitrile and their metal complexes

    NASA Astrophysics Data System (ADS)

    Yang, Jianjie; Shi, Rufei; Zhou, Pei; Qiu, Qiming; Li, Hui

    2016-02-01

    Asymmetric Schiff bases, due to its asymmetric structure, can be used as asymmetric catalyst, antibacterial, and mimic molecules during simulate biological processes, etc. In recent years, research on synthesis and properties of asymmetric Schiff bases have become an increase interest of chemists. This review summarizes asymmetric Schiff bases derived from diaminomaleonitrile (DAMN) and DAMN-based asymmetric Schiff bases metal complexes. Applications of DAMN-based asymmetric Schiff bases are also discussed in this review.

  17. Mechanics of metal-catecholate complexes: the roles of coordination state and metal types.

    PubMed

    Xu, Zhiping

    2013-10-10

    There have been growing evidences for the critical roles of metal-coordination complexes in defining structural and mechanical properties of unmineralized biological materials, including hardness, toughness, and abrasion resistance. Their dynamic (e.g. pH-responsive, self-healable, reversible) properties inspire promising applications of synthetic materials following this concept. However, mechanics of these coordination crosslinks, which lays the ground for predictive and rational material design, has not yet been well addressed. Here we present a first-principles study of representative coordination complexes between metals and catechols. The results show that these crosslinks offer stiffness and strength near a covalent bond, which strongly depend on the coordination state and type of metals. This dependence is discussed by analyzing the nature of bonding between metals and catechols. The responsive mechanics of metal-coordination is further mapped from the single-molecule level to a networked material. The results presented here provide fundamental understanding and principles for material selection in metal-coordination-based applications.

  18. Metal complexes and free radical toxins produced by Pfiesteria piscicida.

    PubMed

    Moeller, Peter D R; Beauchesne, Kevin R; Huncik, Kevin M; Davis, W Clay; Christopher, Steven J; Riggs-Gelasco, Pamela; Gelasco, Andrew K

    2007-02-15

    Metal-containing organic toxins produced by Pfiesteria piscicida were characterized, for the first time, by corroborating data obtained from five distinct instrumental methods: nuclear magnetic resonance spectroscopy (NMR), inductively coupled plasma mass spectrometry (ICP-MS), liquid chromatography particle beam glow discharge mass spectrometry (LC/PB-G DMS), electron paramagnetic resonance spectroscopy (EPR), and X-ray absorption spectroscopy (XAS). The high toxicity of the metal-containing toxins is due to metal-mediated free radical production. This mode of activity explains the toxicity of Pfiesteria, as well as previously reported difficulty in observing the molecular target, due to the ephemeral nature of radical species. The toxins are highly labile in purified form, maintaining activity for only 2-5 days before all activity is lost. The multiple toxin congeners in active extracts are also susceptible to decomposition in the presence of white light, pH variations, and prolonged heat. These findings represent the first formal isolation and characterization of a radical forming toxic organic-ligated metal complex isolated from estuarine/marine dinoflagellates. These findings add to an increased understanding regarding the active role of metals interacting with biological systems in the estuarine environment, as well as their links and implications to human health.

  19. Metal Complexes And Free Radical Toxins Produced By Pfiesteria Piscicida

    SciTech Connect

    Moeller, P.D.R.; Beauchesne, K.R.; Huncik, K.M.; Davis, W.C.; Christopher, S.J.; Riggs-Gelasco, P.; Gelasco, A.K.

    2009-06-03

    Metal-containing organic toxins produced by Pfiesteria piscicida were characterized, for the first time, by corroborating data obtained from five distinct instrumental methods: nuclear magnetic resonance spectroscopy (NMR), inductively coupled plasma mass spectrometry (ICPMS), liquid chromatography particle beam glow discharge mass spectrometry (LC/PB-GDMS), electron paramagnetic resonance spectroscopy (EPR), and X-ray absorption spectroscopy (XAS). The high toxicity of the metal-containing toxins is due to metal-mediated free radical production. This mode of activity explains the toxicity of Pfiesteria, as well as previously reported difficulty in observing the molecular target, due to the ephemeral nature of radical species. The toxins are highly labile in purified form, maintaining activity for only 2-5 days before all activity is lost. The multiple toxin congeners in active extracts are also susceptible to decomposition in the presence of white light, pH variations, and prolonged heat. These findings represent the first formal isolation and characterization of a radical forming toxic organic-ligated metal complex isolated from estuarine/marine dinoflagellates. These findings add to an increased understanding regarding the active role of metals interacting with biological systems in the estuarine environment, as well as their links and implications to human health.

  20. Metal Complexes and Free Radical Toxins Produced by Pfiesteria piscicida

    SciTech Connect

    Moeller,P.; Beauchesne, K.; Huncik, K.; Davis, W.; Christopher, S.; Riggs-Gelasco, P.; Gelasco, A.

    2007-01-01

    Metal-containing organic toxins produced by Pfiesteria piscicida were characterized, for the first time, by corroborating data obtained from five distinct instrumental methods: nuclear magnetic resonance spectroscopy (NMR), inductively coupled plasma mass spectrometry (ICP-MS), liquid chromatography particle beam glow discharge mass spectrometry (LC/PB-GDMS), electron paramagnetic resonance spectroscopy (EPR), and X-ray absorption spectroscopy (XAS). The high toxicity of the metal-containing toxins is due to metal-mediated free radical production. This mode of activity explains the toxicity of Pfiesteria, as well as previously reported difficulty in observing the molecular target, due to the ephemeral nature of radical species. The toxins are highly labile in purified form, maintaining activity for only 2-5 days before all activity is lost. The multiple toxin congeners in active extracts are also susceptible to decomposition in the presence of white light, pH variations, and prolonged heat. These findings represent the first formal isolation and characterization of a radical forming toxic organic-ligated metal complex isolated from estuarine/marine dinoflagellates. These findings add to an increased understanding regarding the active role of metals interacting with biological systems in the estuarine environment, as well as their links and implications to human health.

  1. Multi criteria anisotropic adaptive remeshing for sheet metal forming in FORGE®

    NASA Astrophysics Data System (ADS)

    Perchat, Etienne; François, Guillaume; Coupez, Thierry

    2013-12-01

    In this paper we present an innovative automatic adaptive anisotropic remeshing technique that has been introduced in the commercial FEM software FORGE®. It enables the full 3D simulation of industrial applications of parts with a high aspect ratio such as sheets. An anisotropic mesh is generated in order to adapt to the part and tools geometries, and in order to minimize interpolation error on the velocity field and/or on any other user defined function (eg. temperature, strain …). By minimizing the estimated error, the anisotropic adapted meshes provide a highly accurate solution, often better than those obtained on globally-refined isotropic meshes and at a much lower cost due to the small total number of nodes..

  2. Contact Modelling in Isogeometric Analysis: Application to Sheet Metal Forming Processes

    NASA Astrophysics Data System (ADS)

    Cardoso, Rui P. R.; Adetoro, O. B.; Adan, D.

    2016-08-01

    Isogeometric Analysis (IGA) has been growing in popularity in the past few years essentially due to the extra flexibility it introduces with the use of higher degrees in the basis functions leading to higher convergence rates. IGA also offers the capability of easily reproducing discontinuous displacement and/or strain fields by just manipulating the multiplicity of the knot parametric coordinates. Another advantage of IGA is that it uses the Non-Uniform Rational B-Splines (NURBS) basis functions, that are very common in CAD solid modelling, and consequently it makes easier the transition from CAD models to numerical analysis. In this work it is explored the contact analysis in IGA for both implicit and explicit time integration schemes. Special focus will be given on contact search and contact detection techniques under NURBS patches for both the rigid tools and the deformed sheet blank.

  3. Effectiveness of Rotation-free Triangular and Quadrilateral Shell Elements in Sheet-metal Forming Simulations

    NASA Astrophysics Data System (ADS)

    Brunet, M.; Sabourin, F.

    2005-08-01

    This paper is concerned with the effectiveness of triangular 3-node shell element without rotational d.o.f. and the extension to a new 4-node quadrilateral shell element called S4 with only 3 translational degrees of freedom per node and one-point integration. The curvatures are computed resorting to the surrounding elements. Extension from rotation-free triangular element to a quadrilateral element requires internal curvatures in order to avoid singular bending stiffness. Two numerical examples with regular and irregular meshes are performed to show the convergence and accuracy. Deep-drawing of a box, spring-back analysis of a U-shape strip sheet and the crash simulation of a beam-box complete the demonstration of the bending capabilities of the proposed rotation-free triangular and quadrilateral elements.

  4. Effectiveness of Rotation-free Triangular and Quadrilateral Shell Elements in Sheet-metal Forming Simulations

    SciTech Connect

    Brunet, M.; Sabourin, F.

    2005-08-05

    This paper is concerned with the effectiveness of triangular 3-node shell element without rotational d.o.f. and the extension to a new 4-node quadrilateral shell element called S4 with only 3 translational degrees of freedom per node and one-point integration. The curvatures are computed resorting to the surrounding elements. Extension from rotation-free triangular element to a quadrilateral element requires internal curvatures in order to avoid singular bending stiffness. Two numerical examples with regular and irregular meshes are performed to show the convergence and accuracy. Deep-drawing of a box, spring-back analysis of a U-shape strip sheet and the crash simulation of a beam-box complete the demonstration of the bending capabilities of the proposed rotation-free triangular and quadrilateral elements.

  5. Investigating the Pulse Mode Laser Joining of Overlapped Plastic and Metal Sheets

    NASA Astrophysics Data System (ADS)

    Bauernhuber, Andor; Markovits, Tamás; Takács, János

    The growing utilization of plastic materials in our devices calls for joining them with traditional, often applied structural materials, like metals. Laser assisted metal plastic joining can be used to solve the problem mentioned above, however, relatively few materials have been investigated which could be used to create this special joint. In the course of this research, authors used pulse mode Nd:YAG laser source, structural steel and poly(methyl methacrylate) to create joining between rarely examined material pairs so far, and to explore the effects of technological settings like laser pulse shape, laser spot size, welding speed and joint strength. Material surfaces were also modified (sand blasting,) to enhance joint properties. In plastic material during joining and torn surfaces were investigated. Joints with good strength results were prepared to enable further research on transparent-absorbent metal plastic joining.

  6. Late transition metal m-or chemistry and D6 metal complex photoeliminations

    SciTech Connect

    Sharp, Paul

    2015-07-31

    With the goal of understanding and controlling photoreductive elimination reactions from d6 transition metal complexes as part of a solar energy storage cycle we have investigated the photochemistry of Pt(IV) bromo, chloro, hydroxo, and hydroperoxo complexes. Photoreductive elimination reactions occur for all of these complexes and appear to involve initial Pt-Br, Pt-Cl, or Pt-O bond fission. In the case of Pt-OH bond fission, the subsequent chemistry can be controlled through hydrogen bonding to the hydroxo group.

  7. Metal complexes of cyclic tetra-azatetra-acetic acids.

    PubMed

    Delgado, R; da Silva, J J

    1982-10-01

    The cyclic tetra-aza complexones cDOTA ([12]ane N(4).4ac), cTRITA ([13]ane N(4).4ac) and cTETA ([14]ane N(4).4ac) have been synthesized and characterized by elemental analysis, titration, melting-point determination and NMR (and infrared) spectroscopy. The ionization constants and the stability constants of the MH(2)L, MHL and ML complexes formed with alkali, alkaline-earth and some transition metals were determined at 25.0 +/- 0.1 degrees and ionic strength 0.10M [KNO(3) and (CH(3))(4)NNO(3)]. It was confirmed that cDOTA forms the most stable Ca(2+) and Sr(2+) complexes but the reported inversion of the order of stability of the complexes of these two ions with cTRITA was not confirmed. Also, the values of the stability constants determined in this work differ substantially from those previously reported for ML species. cDOTA is an interesting alternative to classical non-cyclic complex-ones for the complexometric determination of Ca(2+) and Mg(2+) but neither this ligand nor the other two offer advantages over EDTA or DCTA for the complexometric titration of transition metals.

  8. High-density monolayers of metal complexes: preparation and catalysis.

    PubMed

    Hara, Kenji; Sawamura, Masaya; Fukuoka, Atsushi

    2014-10-01

    Catalysts are one of the key materials for realizing a sustainable society. However, we may encounter problematic cases where conventional catalyst systems cannot provide effective solutions. We thus believe that the establishment of novel methods of catalyst preparation is currently necessary. Utilization of high-density monolayers of molecular metal complexes is our strategy, and we expect that this methodology will enable facile and systematic screening of unique and efficient catalysts. This Personal Account describes our challenges to establish such an immature method in catalyst preparation as well as the related background and perspective. Preparation and catalysis by high-density monolayers of Rh complexes with N-heterocyclic carbene, structurally compact phosphine and diisocyanide ligands on gold surfaces are presented. The catalytic application of a high-density Pd-bisoxazoline complex prepared on a single-crystal silicon surface is also shown. Uniquely high catalyst turnover numbers and high chemoselectivities were observed with these catalyst systems.

  9. Infrared Spectroscopy of Metal Ion Complexes: Models for Metal Ligand Interactions and Solvation

    NASA Astrophysics Data System (ADS)

    Duncan, Michael

    2006-03-01

    Weakly bound complexes of the form M^+-Lx (M=Fe, Ni, Co, etc.; L=CO2, C2H2, H2O, benzene, N2) are prepared in supersonic molecular beams by laser vaporization in a pulsed-nozzle cluster source. These species are mass analyzed and size-selected in a reflectron time-of-flight mass spectrometer. Clusters are photodissociated at infrared wavelengths with a Nd:YAG pumped infrared optical parametric oscillator/amplifier (OPO/OPA) laser or with a tunable infrared free-electron laser. M^+-(CO2)x complexes absorb near the free CO2 asymmetric stretch near 2349 cm-1 but with an interesting size dependent variation in the resonances. Small clusters have blue-shifted resonances, while larger complexes have additional bands due to surface CO2 molecules not attached to the metal. M^+(C2H2)n complexes absorb near the C-H stretches in acetylene, but resonances in metal complexes are red-shifted with repect to the isolated molecule. Ni^+ and Co^+ complexes with acetylene undergo intracluster cyclization reactions to form cyclobutadiene. Transition metal water complexes are studied in the O-H stretch region, and partial rotational structure can be measured. M^+(benzene) and M^+(benzene)2 ions (M=V, Ti, Al) represent half-sandwich and sandwich species, whose spectra are measured near the free benzene modes. These new IR spectra and their assignments will be discussed as well as other new IR spectra for similar complexes.

  10. Metal–Metal Bonding in Uranium–Group 10 Complexes

    PubMed Central

    2016-01-01

    Heterobimetallic complexes containing short uranium–group 10 metal bonds have been prepared from monometallic IUIV(OArP-κ2O,P)3 (2) {[ArPO]− = 2-tert-butyl-4-methyl-6-(diphenylphosphino)phenolate}. The U–M bond in IUIV(μ-OArP-1κ1O,2κ1P)3M0, M = Ni (3–Ni), Pd (3–Pd), and Pt (3–Pt), has been investigated by experimental and DFT computational methods. Comparisons of 3–Ni with two further U–Ni complexes XUIV(μ-OArP-1κ1O,2κ1P)3Ni0, X = Me3SiO (4) and F (5), was also possible via iodide substitution. All complexes were characterized by variable-temperature NMR spectroscopy, electrochemistry, and single crystal X-ray diffraction. The U–M bonds are significantly shorter than any other crystallographically characterized d–f-block bimetallic, even though the ligand flexes to allow a variable U–M separation. Excellent agreement is found between the experimental and computed structures for 3–Ni and 3–Pd. Natural population analysis and natural localized molecular orbital (NLMO) compositions indicate that U employs both 5f and 6d orbitals in covalent bonding to a significant extent. Quantum theory of atoms-in-molecules analysis reveals U–M bond critical point properties typical of metallic bonding and a larger delocalization index (bond order) for the less polar U–Ni bond than U–Pd. Electrochemical studies agree with the computational analyses and the X-ray structural data for the U–X adducts 3–Ni, 4, and 5. The data show a trend in uranium–metal bond strength that decreases from 3–Ni down to 3–Pt and suggest that exchanging the iodide for a fluoride strengthens the metal–metal bond. Despite short U–TM (transition metal) distances, four other computational approaches also suggest low U–TM bond orders, reflecting highly transition metal localized valence NLMOs. These are more so for 3–Pd than 3–Ni, consistent with slightly larger U–TM bond orders in the latter. Computational studies of the model systems (PH3)3MU(OH)3I

  11. Aircraft Assembly, Riveting and Surface Repair 2; Sheet Metal Work 2: 9855.03.

    ERIC Educational Resources Information Center

    Dade County Public Schools, Miami, FL.

    This course provides experience in assembly techniques, including repairs on aircraft structures, utilizing all methods from basic layout to surface protection of finished parts. Course content includes goals, specific objectives, metal fasteners, general structural repairs, and aircraft assembly. A bibliography and post-test are appended. Prior…

  12. Continuous process for forming sheet metal from an alloy containing non-dendritic primary solid

    DOEpatents

    Flemings, Merton C.; Matsuniya, Tooru

    1983-01-01

    A homogeneous mixture of liquid-solid metal is shaped by passing the composition from an agitation zone onto a surface moving relative to the exit of the agitation zone. A portion of the composition contacting the moving surface is solidified and the entire composition then is formed.

  13. Numerical Method to Analyze Local Stiffness of the Workpiece to avoid Rebound During Electromagnetic Sheet Metal Forming

    SciTech Connect

    Risch, Desiree; Brosius, Alexander; Psyk, Verena; Kleiner, Matthias

    2007-04-07

    Electromagnetic sheet metal forming is a high speed forming process using pulsed magnetic fields to form metals with high electrical conductivity such as aluminum. Thereby, workpiece velocities of more than 300 m/s are achievable, which can cause difficulties when forming into a die: the kinetic energy, which is related to the workpiece velocity, must dissipate in a short time slot when the workpiece hits the die; otherwise undesired effects, for example rebound, can occur. One possibility to handle this shortcoming is to locally increase the stiffness of the workpiece. In order to be able to estimate the local stiffness a method is presented which is based on a modal analysis by means of the Finite-Element-Method. For this reason, it is necessary to fractionize the considered geometries into a part-dependent number of segments. These are subsequently analyzed separately to determine regions of low geometrical stiffness. Combined with the process knowledge concerning the velocity distribution within the workpiece over the time, a prediction of the feasibility of the forming process and a target-oriented design of the workpiece geometry will be possible. Numerical results are compared with experimental investigations.

  14. The electronic properties of bare and alkali metal adsorbed two-dimensional GeSi alloy sheet

    NASA Astrophysics Data System (ADS)

    Qiu, Wenhao; Ye, Han; Yu, Zhongyuan; Liu, Yumin

    2016-09-01

    In this paper, the structural and electronic properties of both bare and alkali metal (AM) atoms adsorbed two-dimensional GeSi alloy sheet (GeSiAS) are investigated by means of first-principles calculations. The band gaps of bare GeSiAS are shown slightly opened at Dirac point with the energy dispersion remain linear due to the spin-orbit coupling effect at all concentrations of Ge atoms. For metal adsorption, AM atoms (including Li, Na and K) prefer to occupy the hexagonal hollow site of GeSiAS and the primary chemical bond between AM adatom and GeSiAS is ionic. The adsorption energy has an increase tendency with the increase of the Ge concentration in supercell. Besides, single-side adsorption of AM atoms introduces band gap at Dirac point, which can be tuned by the Ge concentration and the species of AM atoms. The strong relation between the band gaps and the distribution of Si and Ge atoms inside GeSiAS are also demonstrated. The opened band gaps of AM covered GeSiAS range from 14.8 to 269.1 meV along with the effective masses of electrons ranging from 0.013 to 0.109 me, indicating the high tunability of band gap as well as high mobility of carriers. These results provide a development in two-dimensional alloys and show potential applications in novel micro/nano-electronic devices.

  15. 40 CFR 721.4680 - Metal salts of complex inorganic oxyacids (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Metal salts of complex inorganic... New Uses for Specific Chemical Substances § 721.4680 Metal salts of complex inorganic oxyacids... substances identified generically as metal salts of complex inorganic oxyacids (PMNs P-89-576 and...

  16. 40 CFR 721.4680 - Metal salts of complex inorganic oxyacids (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Metal salts of complex inorganic... New Uses for Specific Chemical Substances § 721.4680 Metal salts of complex inorganic oxyacids... substances identified generically as metal salts of complex inorganic oxyacids (PMNs P-89-576 and...

  17. 40 CFR 721.4680 - Metal salts of complex inorganic oxyacids (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Metal salts of complex inorganic... New Uses for Specific Chemical Substances § 721.4680 Metal salts of complex inorganic oxyacids... substances identified generically as metal salts of complex inorganic oxyacids (PMNs P-89-576 and...

  18. 40 CFR 721.4680 - Metal salts of complex inorganic oxyacids (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Metal salts of complex inorganic... New Uses for Specific Chemical Substances § 721.4680 Metal salts of complex inorganic oxyacids... substances identified generically as metal salts of complex inorganic oxyacids (PMNs P-89-576 and...

  19. Complex metal borohydrides: multifunctional materials for energy storage and conversion.

    PubMed

    Mohtadi, Rana; Remhof, Arndt; Jena, Puru

    2016-09-07

    With the limited supply of fossil fuels and their adverse effect on the climate and the environment, it has become a global priority to seek alternate sources of energy that are clean, abundant, and sustainable. While sources such as solar, wind, and hydrogen can meet the world's energy demand, considerable challenges remain to find materials that can store and/or convert energy efficiently. This topical review focuses on one such class of materials, namely, multi-functional complex metal borohydrides that not only have the ability to store sufficient amount of hydrogen to meet the needs of the transportation industry, but also can be used for a new generation of metal ion batteries and solar cells. We discuss the material challenges in all these areas and review the progress that has been made to address them, the issues that still need to be resolved and the outlook for the future.

  20. Complex metallic alloys as new materials for additive manufacturing.

    PubMed

    Kenzari, Samuel; Bonina, David; Marie Dubois, Jean; Fournée, Vincent

    2014-04-01

    Additive manufacturing processes allow freeform fabrication of the physical representation of a three-dimensional computer-aided design (CAD) data model. This area has been expanding rapidly over the last 20 years. It includes several techniques such as selective laser sintering and stereolithography. The range of materials used today is quite restricted while there is a real demand for manufacturing lighter functional parts or parts with improved functional properties. In this article, we summarize recent work performed in this field, introducing new composite materials containing complex metallic alloys. These are mainly Al-based quasicrystalline alloys whose properties differ from those of conventional alloys. The use of these materials allows us to produce light-weight parts consisting of either metal-matrix composites or of polymer-matrix composites with improved properties. Functional parts using these alloys are now commercialized.

  1. Complex metal borohydrides: multifunctional materials for energy storage and conversion

    NASA Astrophysics Data System (ADS)

    Mohtadi, Rana; Remhof, Arndt; Jena, Puru

    2016-09-01

    With the limited supply of fossil fuels and their adverse effect on the climate and the environment, it has become a global priority to seek alternate sources of energy that are clean, abundant, and sustainable. While sources such as solar, wind, and hydrogen can meet the world’s energy demand, considerable challenges remain to find materials that can store and/or convert energy efficiently. This topical review focuses on one such class of materials, namely, multi-functional complex metal borohydrides that not only have the ability to store sufficient amount of hydrogen to meet the needs of the transportation industry, but also can be used for a new generation of metal ion batteries and solar cells. We discuss the material challenges in all these areas and review the progress that has been made to address them, the issues that still need to be resolved and the outlook for the future.

  2. Complex metallic alloys as new materials for additive manufacturing

    NASA Astrophysics Data System (ADS)

    Kenzari, Samuel; Bonina, David; Dubois, Jean Marie; Fournée, Vincent

    2014-04-01

    Additive manufacturing processes allow freeform fabrication of the physical representation of a three-dimensional computer-aided design (CAD) data model. This area has been expanding rapidly over the last 20 years. It includes several techniques such as selective laser sintering and stereolithography. The range of materials used today is quite restricted while there is a real demand for manufacturing lighter functional parts or parts with improved functional properties. In this article, we summarize recent work performed in this field, introducing new composite materials containing complex metallic alloys. These are mainly Al-based quasicrystalline alloys whose properties differ from those of conventional alloys. The use of these materials allows us to produce light-weight parts consisting of either metal-matrix composites or of polymer-matrix composites with improved properties. Functional parts using these alloys are now commercialized.

  3. Dynamics of the North American Ice Sheet Complex during its inception and build-up to the Last Glacial Maximum

    NASA Astrophysics Data System (ADS)

    Stokes, Chris R.; Tarasov, Lev; Dyke, Arthur S.

    2012-09-01

    The North American Ice Sheet Complex played a major role in global sea level fluctuations during the Late Quaternary but our knowledge of its dynamics is based mostly on its demise from the Last Glacial Maximum (LGM), a period characterised by non-linear behaviour in the form of punctuated ice margin recession, episodic ice streaming and major shifts in the location of ice divides. In comparison, knowledge of the pre-LGM ice complex is poorly constrained, largely because of the fragmentary nature of the evidence relating to ice sheet build-up. In this paper, we explore the inception and growth of ice (120-20 ka) using a glacial systems model which has been calibrated against a large and diverse set of data relating to the deglacial interval. We make use of calibration data prior to the LGM but its scarcity introduces greater uncertainty, which is partly alleviated by our large ensemble analysis. Results suggest that, following the last interglaciation (Oxygen Isotope Stage: OIS 5e), the ice complex initiated over the north-eastern Canadian Arctic and in the Cordillera within a few thousand years. It then underwent rapid growth to an OIS 5 maximum at ˜110 ka (5d) and covered ˜70% of the area occupied by the LGM ice cover (although only 30% by volume). An OIS 5 minimum is modelled at ˜80 ka (5a), before a second phase of rapid growth at the start of OIS 4, which culminated in a large ice complex at ˜65 ka (almost as large as at the LGM). Subsequent deglaciation was rapid (maximum modelled sea level contribution of >16 cm per century) and resulted in an OIS 3 minimum between ca 55-60 ka. Thereafter, the ice complex grew towards its LGM configuration, interrupted by several phases of successively less significant mass loss. Our results support and extend previous inferences based on geological evidence and reinforce the notion of a highly dynamic pre-LGM ice complex (e.g. with episodes of ±10 s m of eustatic sea level equivalent in <5 ka). Consistent with previous

  4. Chemical bonding of hydrogen molecules to transition metal complexes

    SciTech Connect

    Kubas, G.J.

    1990-01-01

    The complex W(CO){sub 3}(PR{sub 3}){sub 2}(H{sub 2}) (CO = carbonyl; PR{sub 3} = organophosphine) was prepared and was found to be a stable crystalline solid under ambient conditions from which the hydrogen can be reversibly removed in vacuum or under an inert atmosphere. The weakly bonded H{sub 2} exchanges easily with D{sub 2}. This complex represents the first stable compound containing intermolecular interaction of a sigma-bond (H-H) with a metal. The primary interaction is reported to be donation of electron density from the H{sub 2} bonding electron pair to a vacant metal d-orbital. A series of complexes of molybdenum of the type Mo(CO)(H{sub 2})(R{sub 2}PCH{sub 2}CH{sub 2}PR{sub 2}){sub 2} were prepared by varying the organophosphine substitutent to demonstrate that it is possible to bond either dihydrogen or dihydride by adjusting the electron-donating properties of the co-ligands. Results of infrared and NMR spectroscopic studies are reported. 20 refs., 5 fig.

  5. An investigation on co-axial water-jet assisted fiber laser cutting of metal sheets

    NASA Astrophysics Data System (ADS)

    Madhukar, Yuvraj K.; Mullick, Suvradip; Nath, Ashish K.

    2016-02-01

    Water assisted laser cutting has received significant attention in recent times with assurance of many advantages than conventional gas assisted laser cutting. A comparative study between co-axial water-jet and gas-jet assisted laser cutting of thin sheets of mild steel (MS) and titanium (Ti) by fiber laser is presented. Fiber laser (1.07 μm wavelength) was utilised because of its low absorption in water. The cut quality was evaluated in terms of average kerf, projected dross height, heat affected zone (HAZ) and cut surface roughness. It was observed that a broad range process parameter could produce consistent cut quality in MS. However, oxygen assisted cutting could produce better quality only with optimised parameters at high laser power and high cutting speed. In Ti cutting the water-jet assisted laser cutting performed better over the entire range of process parameters compared with gas assisted cutting. The specific energy, defined as the amount of laser energy required to remove unit volume of material was found more in case of water-jet assisted laser cutting process. It is mainly due to various losses associated with water assisted laser processing such as absorption of laser energy in water and scattering at the interaction zone.

  6. Comparative Study of Remote Fiber Laser and Water-Jet Guided Laser Cutting of Thin Metal Sheets

    NASA Astrophysics Data System (ADS)

    Hock, Klaus; Adelmann, Benedikt; Hellmann, Ralf

    This article presents a comparison between remote laser cutting with a fiber laser and water-jet guided laser cutting using a 532 nm solid state laser. Complex contours are processed in stainless steel and brass sheets (thickness ≤ 100 μm), respectively. Results for achievable quality and productivity as well as possible applications for both systems are shown and discussed. We sustained dross free cuts with almost no heat affected zone and small kerf width for the water-jet guided process, whereas small dross, notable heat affected zone and varying kerf width where observed for remote cutting. However, process times for the water-jet guided process where considerably higher than those for remote cutting.

  7. Chemistry and Properties of Complex Intermetallics from Metallic Fluxes

    SciTech Connect

    Kanatzidis, Mercouri G.

    2015-03-28

    This project investigated the reaction chemistry and synthesis of new intermetallic materials with complex compositions and structures using metallic fluxes as solvents. It was found that the metallic fluxes offer several key advantages in facilitating the formation and crystal growth of new materials. The fluxes mostly explored were liquid aluminum, gallium and indium. The main purpose of this project was to exploit the potential of metallic fluxes as high temperature solvent for materials discovery in the broad class of intermetallics. This work opened new paths to compound formation. We discovered many new Si (or Ge)-based compounds with novel structures, bonding and physicochemical properties. We created new insights about the reaction chemistry that is responsible for stabilizing the new materials. We also studied the structural and compositional relationships to understand their properties. We investigated the use of Group-13 metals Al, Ga and In as solvents and have generated a wide variety of new results including several new ternary and quaternary materials with fascinating structures and properties as well as new insights as to how these systems are stabilized in the fluxes. The project focused on reactions of metals from the rare earth element family in combination with transition metals with Si and Ge. For example molten gallium has serves both as a reactive and non-reactive solvent in the preparation and crystallization of intermetallics in the system RE/M/Ga/Ge(Si). Molten indium behaves similarly in that it too is an excellent reaction medium, but it gives compounds that are different from those obtained from gallium. Some of the new phase identified in the aluminide class are complex phases and may be present in many advanced Al-matrix alloys. Such phases play a key role in determining (either beneficially or detrimentally) the mechanical properties of advanced Al-matrix alloys. This project enhanced our basic knowledge of the solid state chemistry

  8. PNP-Pincer-Type Phosphaalkene Complexes of Late Transition Metals.

    PubMed

    Ozawa, Fumiyuki; Nakajima, Yumiko

    2016-10-01

    This account summarizes our recent studies on PNP-pincer-type phosphaalkene complexes. Phosphaalkenes with a P=C bond possess an extremely low-lying π* orbital and have a marked tendency to engage in strong π back-bonding with transition metals. This particular ligand property provides PNP-pincer complexes with unique structures and reactivities. 2,6-Bis(phosphaethenyl)pyridine leads to the isolation of coordinatively unsaturated complexes of Fe(I) and Cu(I); the former adopts a trigonal monopyramidal configuration, whereas the latter has a strong affinity for PF6- and SbF6- as non-coordinating anions. Unsymmetrical PNP-pincer-type phosphaalkene complexes of Ir(I) bearing a dearomatized pyridine unit instantly cleave the N-H bond of NH3 and the C-H bond of MeCN at room temperature. The dearomatized iridium complexes catalyze the dehydrative coupling of amines with alcohols to afford N-alkylated amines and imines in high yields.

  9. Dynamic heteroleptic metal-phenanthroline complexes: from structure to function.

    PubMed

    Saha, Manik Lal; Neogi, Subhadip; Schmittel, Michael

    2014-03-14

    Dynamically heteroligated metal centres are auspicious platforms to access multicomponent supramolecular systems, the latter showing unique structures, amazing properties and even emergent functions. The great potential of heteroleptic complexes has materialised after the development of appropriate strategies that warrant quantitative formation in spite of the dynamic character. In this perspective, we discuss our endeavours at developing various heteroleptic self-assembly protocols based on sterically bulky 2,9-diarylphenanthrolines and our work toward self-sorted multicomponent architectures and assemblies with new and useful functions.

  10. Rationally designed, polymeric, extended metal-ciprofloxacin complexes.

    PubMed

    Xiao, Dong-Rong; Wang, En-Bo; An, Hai-Yan; Su, Zhong-Min; Li, Yang-Guang; Gao, Lei; Sun, Chun-Yan; Xu, Lin

    2005-11-04

    Reactions of the antimicrobial fluoroquinolone ciprofloxacin (cfH) with metal salts in the presence of aromatic polycarboxylate ligands or under basic conditions produce fourteen new metal-cfH complexes, namely, [Ba2(cf)2(1,4-bdc)(H2O)2] x H2O (1), [Sr6(cf)6(1,4-bdc)3(H2O)6] x 2H2O (2), [M2(cfH)2(bptc)(H2O)2] x 8H2O (M = Mn3 and Cd4), [M(cfH)(1,3-bdc)] (M = Mn5, Co6, and Zn7), [Zn2(cfH)4(1,4-bdc)](1,4-bdc) x 13H2O (8), [Ca(cfH)2(1,2-Hbdc)2] x 2H2O (9) and [M(cf)2] x 2.5H2O (M = Mn10, Co11, Zn12, Cd13, and Mg14) (1,4-bdc = 1,4-benzenedicarboxylate, bptc = 3,3',4,4'-benzophenonetetracarboxylate, 1,3-bdc = 1,3-benzenedicarboxylate, 1,2-bdc = 1,2-benzenedicarboxylate). Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric analyses. The structures of 1 and 2 consist of unique two-dimensional arm-shaped layers. Compounds 3 and 4 are isostructural and feature one-dimensional structures formed from the interconnection of [M2(cfH)2(H2O)2] dimers with bptc ligands. Compounds 5-7 are isostructural and contain double-chain-like ribbons constructed from [M2(cfH)2(CO2)2] dimers and 1,3-bdc. Compound 8 consists of a pair of [Zn(cfH)2]2+ fragments bridged by a 1,4-bdc into a dinuclear dumbbell structure. Compound 9 is a neutral monomeric complex. To the best of our knowledge, compounds 1-9 are the first examples of metal-quinolone complexes that contain aromatic polycarboxylate ligands. Compounds 10-14 are isostructural and exhibit interesting two-dimensional rhombic grids featuring large cavities with dimensions of 13.6x13.6 A. Up to now, polymeric extended metal-cfH complexes have never been reported.

  11. Synthesis and luminescence of some rare earth metal complexes

    NASA Astrophysics Data System (ADS)

    Bochkarev, Mikhail N.; Pushkarev, Anatoly P.

    2016-12-01

    In the present paper the synthesis, photoand electroluminescent properties of new rare earth metal complexes prepared and studied at the Razuvaev Institute of Organometallic Chemistry during the last decade are reviewed. The obtained compounds give luminescence in UV, visible and NIR regions. The substituted phenolates, naphtholates, mercaptobenzothiazolate, 8-oxyquinolinolate, polyfluorinated alcoholates and chalcogenophosphinates were used as ligands. The synthesis and structure of unusual three-nuclear sulfidenitride clusters of Nd and Dy are described. The new excitation mechanism of ytterbium phenolates and naphtholates, which includes the stage of reversible reduction of Yb to divalent state and oxidation of the ligands in the excitation process, is discussed.

  12. Long tailed cage amines: Synthesis, metal complexation, and structure

    SciTech Connect

    Dittrich, Birger; Harrowfield, Jack M.; Koutsantonis, George A.; Nealon, Gareth L.; Skelton, Brian W.

    2011-12-09

    The generation of amphiphiles derived from macrobicyclic hexamines of the 'sarcophagine' class can be prepared through efficient and selective reactions involving the reductive alkylation, using long-chain aldehydes, of amino-functionalized sarcophagines when bound to Cu(II) or Mg(II). The Mg(II) pathway is particularly convenient for the ultimate isolation of the free ligands, which can then be used to form metalloamphiphiles with a variety of metal ions. Structural studies have been made of one of the free (protonated) ligands and some of their complexes.

  13. The DNA-binding and bioactivity of rare earth metal complexes.

    PubMed

    Yang, Li; Wang, Bochu; Tan, Jun; Zhu, Liancai

    2013-08-01

    Recently more and more attention is paid to the rare earth metal complexes, because the properties of the rare earth metals are similar to those of the transition metals such as the similar atomic and the ionic radius. A large number of rare metal complexes were synthesized, and their bioactivities were also studied. This review highlights recent researches on the interaction of some rare earth metal complexes with DNA, analyzes how the configuration of the complexes influences the binding affinity, and focuses on the pharmacological activities of the complexes, such as anticancer, antibacterial, antioxidant, anti-inflammatory and anti-virus.

  14. Complexing agent and heavy metal removals from metal plating effluent by electrocoagulation with stainless steel electrodes.

    PubMed

    Kabdaşli, Işik; Arslan, Tülin; Olmez-Hanci, Tuğba; Arslan-Alaton, Idil; Tünay, Olcay

    2009-06-15

    In the present study, the treatability of a metal plating wastewater containing complexed metals originating from the nickel and zinc plating process by electrocoagulation using stainless steel electrodes was experimentally investigated. The study focused on the effect of important operation parameters on electrocoagulation process performance in terms of organic complex former, nickel and zinc removals as well as sludge production and specific energy consumption. The results indicated that increasing the applied current density from 2.25 to 9.0 mA/cm(2) appreciably enhanced TOC removal efficiency from 20% to 66%, but a further increase in the applied current density to 56.25 mA/cm(2) did not accelerate TOC removal rates. Electrolyte concentration did not affect the process performance significantly and the highest TOC reduction (66%) accompanied with complete heavy metal removals were achieved at the original chloride content ( approximately 1500 mg Cl/L) of the wastewater sample. Nickel removal performance was adversely affected by the decrease of initial pH from its original value of 6. Optimum working conditions for electrocoagulation of metal plating effluent were established as follows: an applied current density of 9 mA/cm(2), the effluent's original electrolyte concentration and pH of the composite sample. TOC removal rates obtained for all electrocoagulation runs fitted pseudo-first-order kinetics very well (R(2)>92-99).

  15. Simulation of the mobility of metal - EDTA complexes in groundwater: The influence of contaminant metals

    USGS Publications Warehouse

    Friedly, J.C.; Kent, D.B.; Davis, J.A.

    2002-01-01

    Reactive transport simulations were conducted to model chemical reactions between metal - EDTA (ethylenediaminetetraacetic acid) complexes during transport in a mildly acidic quartz - sand aquifer. Simulations were compared with the results of small-scale tracer tests wherein nickel-, zinc-, and calcium - EDTA complexes and free EDTA were injected into three distinct chemical zones of a plume of sewage-contaminated groundwater. One zone had a large mass of adsorbed, sewage-derived zinc; one zone had a large mass of adsorbed manganese resulting from mildly reducing conditions created bythe sewage plume; and one zone had significantly less adsorbed manganese and negligible zinc background. The chemical model assumed that the dissolution of iron(III) from metal - hydroxypolymer coatings on the aquifer sediments by the metal - EDTA complexes was kinetically restricted. All other reactions, including metal - EDTA complexation, zinc and manganese adsorption, and aluminum hydroxide dissolution were assumed to reach equilibrium on the time scale of transport; equilibrium constants were either taken from the literature or determined independently in the laboratory. A single iron(III) dissolution rate constant was used to fit the breakthrough curves observed in the zone with negligible zinc background. Simulation results agreed well with the experimental data in all three zones, which included temporal moments derived from breakthrough curves at different distances downgradient from the injections and spatial moments calculated from synoptic samplings conducted at different times. Results show that the tracer cloud was near equilibrium with respect to Fe in the sediment after 11 m of transport in the Zn-contaminated region but remained far from equilibrium in the other two zones. Sensitivity studies showed that the relative rate of iron(III) dissolution by the different metal - EDTA complexes was less important than the fact that these reactions are rate controlled. Results

  16. Simulation of the mobility of metal-EDTA complexes in groundwater: the influence of contaminant metals.

    PubMed

    Friedly, J C; Kent, D B; Davis, J A

    2002-02-01

    Reactive transport simulations were conducted to model chemical reactions between metal-EDTA (ethylenediaminetetraacetic acid) complexes during transport in a mildly acidic quartz-sand aquifer. Simulations were compared with the results of small-scale tracer tests wherein nickel-, zinc-, and calcium-EDTA complexes and free EDTA were injected into three distinct chemical zones of a plume of sewage-contaminated groundwater. One zone had a large mass of adsorbed, sewage-derived zinc; one zone had a large mass of adsorbed manganese resulting from mildly reducing conditions created by the sewage plume; and one zone had significantly less adsorbed manganese and negligible zinc background. The chemical model assumed that the dissolution of iron(III) from metal-hydroxypolymer coatings on the aquifer sediments by the metal-EDTA complexes was kinetically restricted. All other reactions, including metal-EDTA complexation, zinc and manganese adsorption, and aluminum hydroxide dissolution were assumed to reach equilibrium on the time scale of transport; equilibrium constants were either taken from the literature or determined independently in the laboratory. A single iron(III) dissolution rate constant was used to fit the breakthrough curves observed in the zone with negligible zinc background. Simulation results agreed well with the experimental data in all three zones, which included temporal moments derived from breakthrough curves at different distances downgradient from the injections and spatial moments calculated from synoptic samplings conducted at different times. Results show that the tracer cloud was near equilibrium with respect to Fe in the sediment after 11 m of transport in the Zn-contaminated region but remained far from equilibrium in the other two zones. Sensitivity studies showed that the relative rate of iron(III) dissolution by the different metal-EDTA complexes was less important than the fact that these reactions are rate controlled. Results suggest that

  17. Assembly of three novel metal (II) complexes based on polycarboxylate and 1,10-phenanthroline ligands

    NASA Astrophysics Data System (ADS)

    Chen, Xiaoli; Qiao, Yali; Gao, Loujun; Cui, Huali; Zhang, Meili; Lv, Junfang

    2013-04-01

    With the principles of crystal engineering, three novel metal(II) complexes, [Cu2(betd)(phen)4].15H2O (1), [Cd4(betd)2(phen)8]ṡ28H2O (2) and {[Co2(betd)(phen)2(H2O)2]·2H2O}n (3) (H4betd = bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid, phen = 1,10-phenanthroline) were synthesized and structurally characterized by elemental analyses, IR spectroscopy, single-crystal X-ray diffraction analyses, TGA, powder XRD and fluorescent measurements. Complex 1 is a binuclear structure, novel water tapes are observed to be encapsulated in the 3D open supramolecular architecture by hydrogen bond interactions. In 2, two pairs of CdII ions joined with two (betd)4- ions to form a cyclic tetranuclear structure. The neighboring tetranuclear units are linked into 2D network through π⋯π stacking interactions. Interestingly, the lattice H2O molecules are joined by strong hydrogen bond interactions generating a wavy water layer, which contacts the 2D network to form 3D supramolecular structure. 3 shows a 2D (4, 4) grid network, which are assembled in an ABAB sequence to 3D supramolecular structures via π⋯π stacking interactions between two central phen ligands from two adjacent sheets and hydrogen bond interactions.

  18. Half-metallic and magnetic properties in nonmagnetic element embedded graphitic carbon nitride sheets.

    PubMed

    Meng, Bo; Xiao, Wen-zhi; Wang, Ling-ling; Yue, Li; Zhang, Song; Zhang, Hong-yun

    2015-09-14

    We have investigated the structures, electronic structures and magnetic properties of the triazine-based g-C3N4 (gt-C3N4) monolayer doped with B, Al, and Cu atoms based on density functional theory using ab initio calculations. The B atom prefers to be situated at the center of the triazine ring, whereas the Al and Cu atoms tend to be located above the center of the triazine ring. The doping at the interstitial sites results in nonplanar structures which are thermodynamically stable. Each dopant atom induces a total magnetic moment of 1.0 μB which mainly arises from the pz orbitals because the n-type doping injects unpaired electrons into anti-π orbitals. The results obtained from the GGA-PBE and HSE06 schemes show that all the doped systems exhibit half-metallic behaviors. B- and Al-doped systems are at a ferromagnetic ground state, while the Cu-doped case is at an anti-ferromagnetic ground state. The long-range half-metallic ferromagnetic order is attributed to the p-p interactions. In particular, the estimated Curie temperature implies that the systems doped with B are potential candidates for spintronics applications in future.

  19. Current Sheets in the Corona and the Complexity of Slow Wind

    NASA Technical Reports Server (NTRS)

    Antiochos, Spiro

    2010-01-01

    The origin of the slow solar wind has long been one of the most important problems in solar/heliospheric physics. Two observational constraints make this problem especially challenging. First, the slow wind has the composition of the closed-field corona, unlike the fast wind that originates on open field lines. Second, the slow wind has substantial angular extent, of order 30 degrees, which is much larger than the widths observed for streamer stalks or the widths expected theoretically for a dynamic heliospheric current sheet. We propose that the slow wind originates from an intricate network of narrow (possibly singular) open-field corridors that emanate from the polar coronal hole regions. Using topological arguments, we show that these corridors must be ubiquitous in the solar corona. The total solar eclipse in August 2008, near the lowest point of cycle 23 affords an ideal opportunity to test this theory by using the ultra-high resolution Predictive Science's (PSI) eclipse model for the corona and wind. Analysis of the PSI eclipse model demonstrates that the extent and scales of the open-field corridors can account for both the angular width of the slow wind and its closed-field composition. We discuss the implications of our slow wind theory for the structure of the corona and heliosphere at solar minimum and describe further observational and theoretical tests.

  20. Externally controlled spin state switching in metal-organic complexes.

    NASA Astrophysics Data System (ADS)

    Bagrets, Alexei; Meded, Velimir; Ruben, Mario; Evers, Ferdinand

    2009-03-01

    Recent transport experiments have demonstrated that a manipulation of the charge of individual molecules is feasible using electromigrated metal junctions [1] or electrochemical gates in conjunction with the STM [2]. Using elaborated density functional theory calculations, we will discuss a possibility to induce -- by means of charging or applied stress -- a switching between low and high spin states in certain metal-organic systems, [Fe(bpp)2]^2+ (bpp: bispyrazolyl pyridine) and [Mn(tpy)2]^2+ (tpy: terpyridine). Based upon a recent success of the single molecular conduction experiment through Ru(II) complex [3], we anticipate the transport properties of Fe(II) and Mn(II) complexes to be gate controlled via exploiting their spin degree of freedom. [1] E. A. Osorio et al., J. Phys.: Condens. Matter20, 374121 (2008); [2] F. Chen el al., Ann. Rev. Phys. Chem. 58, 535 (2007); Li et al., Nanotechnology 18, 044018 (2007). [3] M. Ruben, A. Landa, E. L"ortscher, H. Riel, M. Mayor, H. G"orls, H. Weber, A. Arnold, and F. Evers, Small (online), DOI: 10.1002/smll.200800390 (2008).

  1. Prediction of inhomogeneous texture in clad sheet metals by hot roll bond method

    NASA Astrophysics Data System (ADS)

    Choi, Shi-Hoon; Kwon, Jae Wook; Oh, Kyu Hwan

    1996-06-01

    A finite element analysis was applied to analyze the evolution of an inhomogeneity of rolling texture in hot rolled clad metal with Taylor-Bishop-Hill model and Renourd-Winterberger method. The shear texture has been developed in the surface layer of the aluminum and plane strain texture has been developed in the center layer. The calculated texture variations through thickness direction could simulate experimental texture using deformation gradient from FEM. The ratio of shear strain to rolling strain, x, which represents the degree of rotation about transverse direction could give the degree of development of shear texture. The larger value of x gives the larger crystal rotation about transverse direction and subsequently the development of shear texture. The calculated (111) pole figures were in good agreement with experimentally measured pole figures.

  2. Dipyridyl β-diketonate complexes and their use as metalloligands in the formation of mixed-metal coordination networks.

    PubMed

    Burrows, Andrew D; Mahon, Mary F; Renouf, Catherine L; Richardson, Christopher; Warren, Anna J; Warren, John E

    2012-04-14

    The iron(III) and aluminium(III) complexes of 1,3-di(4-pyridyl)propane-1,3-dionato (dppd) and 1,3-di(3-pyridyl)propane-1,3-dionato (dmppd), [Fe(dppd)(3)] 1, [Fe(dmppd)(3)] 2, [Al(dppd)(3)] 3 and [Al(dmppd)(3)] 4 have been prepared. These complexes adopt molecular structures in which the metal centres contain distorted octahedral geometries. In contrast, the copper(II) and zinc(II) complexes [Cu(dppd)(2)] 5 and [Zn(dmppd)(2)] 6 both form polymeric structures in which coordination of the pyridyl groups into the axial positions of neighbouring metal centres links discrete square-planar complexes into two-dimensional networks. The europium complex [Eu(dmppd)(2)(H(2)O)(4)]Cl·2EtOH·0.5H(2)O 7 forms a structure containing discrete cations that are linked into sheets through hydrogen bonds, whereas the lanthanum complex [La(dmppd)(3)(H(2)O)]·2H(2)O 8 adopts a one-dimensional network structure, connected into sheets by hydrogen bonds. The iron complexes 1 and 2 act as metalloligands in reactions with silver(I) salts, with the nature of the product depending on the counter-ions present. Thus, the reaction between 1 and AgBF(4) gave [AgFe(dppd)(3)]BF(4)·DMSO 9, in which the silver centres link the metalloligands into discrete nanotubes, whereas reactions with AgPF(6) and AgSbF(6) gave [AgFe(dppd)(3)]PF(6)·3.28DMSO 10 and [AgFe(dppd)(3)]SbF(6)·1.25DMSO 11, in which the metalloligands are linked into sheets. In all three cases, only four of the six pyridyl groups present on the metalloligands are coordinated. The reaction between 2 and AgNO(3) gave [Ag(2)Fe(dmppd)(3)(ONO(2))]NO(3)·MeCN·CH(2)Cl(2)12. Compound 12 adopts a layer structure in which all pyridyl groups are coordinated to silver centres and, in addition, a nitrate ion bridges between two silver centres. A similar structure is adopted by [Ag(2)Fe(dmppd)(3)(O(2)CCF(3))]CF(3)CO(2)·2MeCN·0.25CH(2)Cl(2)13, with a bridging trifluoroacetate ion playing the same role as the nitrate ion in 12.

  3. Studies of Transition Metal Complexes Using Dynamic NMR Techniques.

    NASA Astrophysics Data System (ADS)

    Coston, Timothy Peter John

    Available from UMI in association with The British Library. This Thesis is primarily concerned with the quantitative study of fluxional processes in, predominantly platinum(IV) complexes, with the ligands 1,1,2,2-tetrakis(methylthio)ethane (MeS)_2CHCH(SMe)_2 , and 1,1,2,2-tetrakis(methylthio)ethene (MeS) _2C=C(SMe)_2. Quantitative information relating to the energetics of these processes has been obtained by a combination of one- and two-dimensional NMR techniques. Chapter One provides an introduction to the background of fluxional processes in transition metal complexes together with data concerning the energetics of the processes that have already been studied by NMR techniques. Chapter Two provides a thorough grounding in NMR techniques, in particular those concerned with the quantitative measurement of rates involved in chemical exchange processes. A description of the use of 2D EXSY NMR spectroscopy in obtaining rate data is given. The properties of the magnetic isotope of platinum are given in Chapter Three. A general survey is also given of some additional compounds that have already been studied by platinum-195 spectroscopy. Chapter Four is concerned with the quantitative study of low temperature (<293 K) fluxionality (sulphur inversion) in the complexes (PtXMe_3 (MeS)_2CHCH(SMe) _2) (X = Cl, Br, I). These complexes were studied by dynamic nuclear magnetic resonance and the information regarding the rates of sulphur inversion was obtained by complete band-shape analysis. Chapter Five is concerned with high temperature (>333 K) fluxionality, of the previous complexes, as studied by a combination of one- and two -dimensional NMR techniques. Aside from obtaining thermodynamic parameters for all the processes, a new novel mechanism is proposed. Chapter Six is primarily concerned with the NMR investigation of the new dinuclear complexes ((PtXMe _3)_2(MeS) _2CHCH(SMe)_2) (X = Cl, Br, I). The solution properties have been established and thermo-dynamic parameters

  4. 3D cone-sheet and crystal-settling models reveal magma-reservoir structure of the Carlingford central complex, Ireland

    NASA Astrophysics Data System (ADS)

    Schauroth, Jenny; Burchardt, Steffi; Meade, Fiona; Troll, Valentin R.

    2014-05-01

    The Palaeogene Carlingford central complex, northeast Ireland, hosts a swarm of mostly basaltic cone-sheets with several lithological subsets (Halsall, 1974). The two most abundant sets are aphyric and highly porphyritic cone-sheets with up to 80% of cm-sized plagioclase phenocrysts. The abundance of highly porphyritic cone-sheets seems to systematically increase with altitude compared to the aphyric type (Meade, 2008). We hypothesised that this observation might be explained by the zonation of the source magma reservoir. In order to test this hypothesis, we modelled the 3D cone-sheet structure at depth and the settling of plagioclase phenocrysts. The 3D model of the Carlingford cone-sheet swarm reveals that lithological types of Carlingford cone-sheets are not systematically distributed in space. Using the method proposed by Burchardt et al. (2013), we constructed the likely source reservoir of the cone-sheets, which is saucer-shaped, elongated in NW direction, 7 km long and 3 km wide, and located at a depth of 1 km below the present-day land surface. Our calculation of the terminal velocity of the plagioclase phenocrysts shows that the large phenocrysts in the porphyritic cone-sheets were too big to float at the conditions present in the Carlingford magma reservoir. We can therefore exclude vertical magma-chamber stratification as an explanation for the formation and distribution of porphyritic and aphyric cone-sheets. Instead, we envisage the formation of a crystal mush at the base and sides of the Carlingford magma reservoir. Cone-sheet injection and magma-cha,ber replenishments have remobilised plagioclase cumulates, which may explain the occurrence and distribution of aphyric and highly porphyritic cone-sheets. REFERENCES Burchardt, S., Troll, V. R., Mathieu, L., Emeleus, H. C., Donaldson, C., 2013, Scientific Reports 3, 2891. Halsall, T.J., 1974, The minor intrusions and structure of the Carlingford complex, Eire (PhD thesis): University of Leicester. Meade

  5. High load-bearing multi-material-joints of metal sheets and composites by incremental in-situ forming processes

    NASA Astrophysics Data System (ADS)

    Seidlitz, Holger; Fritzsche, Sebastian; Bambach, Markus; Gerstenberger, Colin

    2016-10-01

    Thermo-mechanically flow-formed joints (FDJ) are an appropriate joining technology to realize high load-bearing multi-material-joints between fiber reinforced thermoplastics and sheet metals, without additional joining components. As in the automotive industry new vehicle and lightweight designs with one-sided accessibility joints are required, the technology which so far requires a two-sided accessibility of the joint, is examined for the ability to be performed with one-sided accessibility. The main part of the paper are therefore experimental studies on the one-sided manufacturing of FDJ-joints without an additional forming tool and their examination with head pull test and tension shear test according to DIN EN ISO 14272 and DIN EN ISO 14273. In this context, a tool and an experimental setup were designed to provide a corresponding joint production of a material combination of continuous glass fiber reinforced polypropylene (Plytron) and an aluminum alloy (EN AW-6082 T6). In the experiment, the novel joints bear maximum forces of 291 N in the head pull test and 708 N in the tension shear test.

  6. The impact of metal transport processes on bioavailability of free and complex metal ions in methanogenic granular sludge.

    PubMed

    Bartacek, Jan; Fermoso, Fernando G; Vergeldt, Frank; Gerkema, Edo; Maca, Josef; van As, Henk; Lens, Piet N L

    2012-01-01

    Bioavailability of metals in anaerobic granular sludge has been extensively studied, because it can have a major effect on metal limitation and metal toxicity to microorganisms present in the sludge. Bioavailability of metals can be manipulated by bonding to complexing molecules such as ethylenediaminetetraacetate (EDTA) or diethylenetriaminepentaacetate (DTPA). It has been shown that although the stimulating effect of the complexed metal species (e.g. [CoEDTA](2-)) is very fast, it is not sustainable when applied to metal-limited continuously operated reactors. The present paper describes transport phenomena taking place inside single methanogenic granules when the granules are exposed to various metal species. This was done using magnetic resonance imaging (MRI). The MRI results were subsequently related to technological observations such as changes in methanogenic activity upon cobalt injection into cobalt-limited up-flow anaerobic sludge blanket (UASB) reactors. It was shown that transport of complexed metal species is fast (minutes to tens of minutes) and complexed metal can therefore quickly reach the entire volume of the granule. Free metal species tend to interact with the granular matrix resulting in slower transport (tens of minutes to hours) but higher final metal concentrations.

  7. Composite of liposome and metal complexes: Toward creating a new chemical reaction space

    NASA Astrophysics Data System (ADS)

    Koshiyama, Tomomi; Ohba, Masaaki

    2015-12-01

    The purpose of our research is to construct a novel functional space by fixation of various metal complexes into the liposome space. For the functionalization of liposome surface, we designed lipophilic metal complexes and succeeded in the fixation of various metal complexes such as oxidation catalysts. In addition, reactivities of metal complexes on the liposome surface were optimized by controlling their surrounding environment using various types of phospholipids. Furthermore, we succeeded in the incorporation of coordination polymers in inner water phase of liposomes using antibiotic ion channel, and the composites showed absorption of metal ions through antibiotic ion channels.

  8. Numerical modelling of the gas detonation process of sheet metal forming

    NASA Astrophysics Data System (ADS)

    Patil, Sandeep P.; Popli, Madhur; Jenkouk, Vahid; Markert, Bernd

    2016-08-01

    Gas detonation forming is an unconventional technique, which has the potential to form complex geometries, including sharp angles and undercuts in a very short process time. To date, most of the numerical studies on detonation forming neglect the highly dynamic pressure profile of the detonation obtained from experiments. In the present work, it is emphasised that the consideration of the actual detonation pressure as measured in the experiment is crucial. The thickness distribution and radial strain are studied using a strain-rate dependent Johnson-Cook material model. The obtained results vary significantly with change in loading rate. Moreover, the model is capable of predicting extremely sharp edges.

  9. Hydrogen storage and evolution catalysed by metal hydride complexes.

    PubMed

    Fukuzumi, Shunichi; Suenobu, Tomoyoshi

    2013-01-07

    The storage and evolution of hydrogen are catalysed by appropriate metal hydride complexes. Hydrogenation of carbon dioxide by hydrogen is catalysed by a [C,N] cyclometalated organoiridium complex, [Ir(III)(Cp*)(4-(1H-pyrazol-1-yl-κN(2))benzoic acid-κC(3))(OH(2))](2)SO(4) [Ir-OH(2)](2)SO(4), under atmospheric pressure of H(2) and CO(2) in weakly basic water (pH 7.5) at room temperature. The reverse reaction, i.e., hydrogen evolution from formate, is also catalysed by [Ir-OH(2)](+) in acidic water (pH 2.8) at room temperature. Thus, interconversion between hydrogen and formic acid in water at ambient temperature and pressure has been achieved by using [Ir-OH(2)](+) as an efficient catalyst in both directions depending on pH. The Ir complex [Ir-OH(2)](+) also catalyses regioselective hydrogenation of the oxidised form of β-nicotinamide adenine dinucleotide (NAD(+)) to produce the 1,4-reduced form (NADH) under atmospheric pressure of H(2) at room temperature in weakly basic water. In weakly acidic water, the complex [Ir-OH(2)](+) also catalyses the reverse reaction, i.e., hydrogen evolution from NADH to produce NAD(+) at room temperature. Thus, interconversion between NADH (and H(+)) and NAD(+) (and H(2)) has also been achieved by using [Ir-OH(2)](+) as an efficient catalyst and by changing pH. The iridium hydride complex formed by the reduction of [Ir-OH(2)](+) by H(2) and NADH is responsible for the hydrogen evolution. Photoirradiation (λ > 330 nm) of an aqueous solution of the Ir-hydride complex produced by the reduction of [Ir-OH(2)](+) with alcohols resulted in the quantitative conversion to a unique [C,C] cyclometalated Ir-hydride complex, which can catalyse hydrogen evolution from alcohols in a basic aqueous solution (pH 11.9). The catalytic mechanisms of the hydrogen storage and evolution are discussed by focusing on the reactivity of Ir-hydride complexes.

  10. Oligomeric rare-earth metal cluster complexes with endohedral transition metal atoms

    SciTech Connect

    Steinberg, Simon; Zimmermann, Sina; Brühmann, Matthias; Meyer, Eva; Rustige, Christian; Wolberg, Marike; Daub, Kathrin; Bell, Thomas; Meyer, Gerd

    2014-11-15

    Comproportionation reactions of rare-earth metal trihalides (RX{sub 3}) with the respective rare-earth metals (R) and transition metals (T) led to the formation of 22 oligomeric R cluster halides encapsulating T, in 19 cases for the first time. The structures of these compounds were determined by single-crystal X-ray diffraction and are composed of trimers ((T{sub 3}R{sub 11})X{sub 15}-type, P6{sub 3}/m), tetramers ((T{sub 4}R{sub 16})X{sub 28}(R{sub 4}) (P-43m), (T{sub 4}R{sub 16})X{sub 20} (P4{sub 2}/nnm), (T{sub 4}R{sub 16})X{sub 24}(RX{sub 3}){sub 4} (I4{sub 1}/a) and (T{sub 4}R{sub 16})X{sub 23} (C2/m) types of structure) and pentamers ((Ru{sub 5}La{sub 14}){sub 2}Br{sub 39}, Cc) of (TR{sub r}){sub n} (n=2–5) clusters. These oligomers are further enveloped by inner (X{sup i}) as well as outer (X{sup a}) halido ligands, which possess diverse functionalities and interconnect like oligomers through i–i, i–a and/or a–i bridges. The general features of the crystal structures for these new compounds are discussed and compared to literature entries as well as different structure types with oligomeric T centered R clusters. Dimers and tetramers originating from the aggregation of (TR{sub 6}) octahedra via common edges are more frequent than trimers and pentamers, in which the (TR{sub r}) clusters share common faces. - Graphical abstract: Rare earth-metal cluster complexes with endohedral transition metal atoms (TR{sub 6}) may connect via common edges or faces to form dimers, trimers, tetramers and pentamers of which the tetramers are the most prolific. Packing effects and electron counts play an important role. - Highlights: • Rare-earth metal cluster complexes encapsulate transition metal atoms. • Oligomers are built via connection of octahedral clusters via common edges or faces. • Dimers through pentamers with closed structures are known. • Tetramers including a tetrahedron of endohedral atoms are the most prolific.

  11. Noise emission zones in an automobile sheet-metal pressing plant, a 25-year follow-up study at three locations in the plant.

    PubMed

    Brühl, P; Davidsson, C; Ivarsson, A

    1996-01-01

    The Volvo plant at Olofström, Sweden is engaged in the pressing and assembling of sheet-metal components for automobiles. During the past 25 years, determined efforts have been made to introduce less noisy methods of production and to limit the levels of noise emission in three large workshops at the plant. Noise levels were mapped with the aid of stationary noise measurements. The results are expressed in terms of noise emission zones and presented as noise contour maps. The investigations were made on four occasions between 1967 and 1991. Following the comparative area calculations of the noise emission zones, it was deduced that the noise levels had been significantly reduced, despite an increased production. The results show that noise reduction measures applied to the presses. An increase in automation in sheet-metal handling, improved quality in the pressing of components and changes in the range of products have contributed to the reduction of noise levels at the plant.

  12. The Tolman electronic parameter (TEP) and the metal-metal electronic communication in ditopic NHC complexes.

    PubMed

    Gusev, Dmitry G; Peris, Eduardo

    2013-05-28

    Whereas the electronic communication between metals in dimetallic organometallic compounds is often assessed through cyclic voltammetric measurements, we have found that the variations in the Tolman electronic parameter (TEP) can also be an alternative and effective way of determining this type of interaction. The TEP values of several (CO)3Ni-NHC-X systems with five different ditopic NHC ligand systems [triazolyldiylidene (A), bis(imidazolylidene) (B), benzobis(imidazolylidene) (C), cyclopenta[f,g]acenaphthylenebis(imidazolylidene) (D) and bis(imidazolidinylidene) (F)] were determined by means of DFT calculations. Based on these values, the electron-withdrawing character of the X metal fragments employed in this study was found to increase in the order IrCp(CO) → RhCl(COD) → Ni(CO)3 → Cr(CO)5 → RhCl(CO)2. We found that the degree of electronic interaction through the ditopic NHC ligands is the strongest in A, followed by B and F, while being weak in B and C. The TEP values and the quantitative analysis of the upper molecular orbitals of A and F and their (CO)3Ni-NHC-Ni(CO)3 complexes strongly suggest that the principal electronic interaction between the metal centres of the M-NHC-M' complexes is of σ-type, via the delocalized HOMO and HOMO - 1 orbitals of the NHC ligands.

  13. Complexities of high temperature metal fatigue: Some steps toward understanding

    NASA Technical Reports Server (NTRS)

    Manson, S. S.; Halford, G. R.

    1983-01-01

    After pointing out many of the complexities that attend high temperature metal fatigue beyond those already studied in the sub-creep range, a description of the micromechanisms of deformation and fracture is presented for several classes of materials that were studied over the past dozen years. Strainrange Partitioning (SRP) is used as a framework for interpreting the results. Several generic types of behavior were observed with regard both to deformation and fracture and each is discussed in the context of the micromechanisms involved. Treatment of cumulative fatigue damage and the possibility of ""healing'' of damage in successive loading loops, has led to a new interpretation of the Interaction Damage Rule of SRP. Using the concept of ""equivalent micromechanistic damage'' -- that the same damage on a microscopic scale is induced if the same hysteresis loops are generated, element for element -- it turns out the Interaction Damage Rule essentially compounds a number of variants of hysteresis loops, all of which have the same damage according to SRP concepts, into a set of loops each containing only one of the generic SRP strainranges. Thus the damage associcated with complex loops comprising several types of strainrange is analyzed by considering a combination of loops each containing only one type of strainrange. This concept is expanded to show how several independent loops can combine to ""heal'' creep damage in a complex loading history.

  14. Formability of Al 5xxx Sheet Metals Using Pulsed Current for Various Heat Treatments

    SciTech Connect

    Salandro, Wesley A.; Jones, Joshua J.; McNeal, Timothy A.; Roth, John T.; Hong, Sung Tae; Smith, Mark T.

    2010-10-01

    Previous studies have shown that the presence of a pulsed electrical current, applied during the deformation process of an aluminum specimen, can significantly improve the formability of the aluminum without heating the metal above its maximum operating temperature range. The research herein extends these findings by examining the effect of electrical pulsing on 5052 and 5083 Aluminum Alloys. Two different parameter sets were used while pulsing three different heat treatments (As Is, 398°C, and 510°C) for each of the two aluminum alloys. For this research, the electrical pulsing is applied to the aluminum while the specimens are deformed, without halting the deformation process (a manufacturing technique known as Electrically-Assisted Manufacturing). The analysis focuses on establishing the effect the electrical pulsing has on the aluminum alloy’s various heat treatments by examining the displacement of the material throughout the testing region of dogbone-shaped specimens. The results from this research show that pulsing significantly increases the maximum achievable elongation of the aluminum (when compared to baseline tests conducted without electrical pulsing). Another beneficial effect produced by electrical pulsing is that the engineering flow stress within the material is considerably reduced. The electrical pulses also cause the aluminum to deform non-uniformly, such that the material exhibits a diffuse neck where the minimum deformation occurs near the ends of the specimen (near the clamps) and the maximum deformation occurs near the center of the specimen (where fracture ultimately occurs). This diffuse necking effect is similar to what can be experienced during superplastic deformation. However, when comparing the presence of a diffuse neck in this research, electrical pulsing does not create as significant of a diffuse neck as superplastic deformation. Electrical pulsing has the potential to be more efficient than traditional methods of incremental

  15. Dihydrogen bonding vs metal-σ interaction in complexes between H2 and metal hydride.

    PubMed

    Alkorta, Ibon; Elguero, Jose; Solimannejad, Mohammad; Grabowski, Sławomir J

    2011-01-20

    The complexes formed by hydrogen with metal hydrides (LiH, NaH, BeH(2), MgH(2), BH(3), AlH(3), Li(2)H(2), Na(2)H(2), Be(2)H(4), and Mg(2)H(4)) have been theoretically studied at the MP2/aug-cc-pVTZ, MP2/aug-cc-pVQZ and CCSD(T)/aug-cc-pVTZ//CCSD/aug-cc-pVTZ levels of theory. The hydrogen molecule can act as a Lewis acid or base. In the first case, a dihydrogen bonded complex is obtained and in the second an interaction between the σ-bond of the hydrogen molecule and an empty orbital of the metal atoms is found. Quantum theory of atoms in molecules and natural bond orbitals methods have been applied to analyze the intermolecular interactions. Additionally, the cooperativity effects are analyzed for selected complexes with two H(2) molecules where both kinds of interactions exist simultaneously.

  16. Photochemical reactions of metal nitrosyl complexes. Mechanisms of NO reactions with biologically relevant metal centers

    DOE PAGES

    Ford, Peter C.

    2001-01-01

    Tmore » he discoveries that nitric oxide (a.k.a. nitrogen monoxide) serves important roles in mammalian bioregulation and immunology have stimulated intense interest in the chemistry and biochemistry of NO and derivatives such as metal nitrosyl complexes. Also of interest are strategies to deliver NO to biological targets on demand. One such strategy would be to employ a precursor which displays relatively low thermal reactivity but is photochemically active to release NO.his proposition led us to investigate laser flash and continuous photolysis kinetics of nitrosyl complexes such as the Roussin's iron-sulfur-nitrosyl cluster anions Fe 2 S 2 ( NO ) 4 2 − and Fe 4 S 3 ( NO ) 7 − and several ruthenium salen and porphyrin nitrosyls.hese include studies using metal-nitrosyl photochemistry as a vehicle for delivering NO to hypoxic cell cultures in order to sensitize γ -radiation damage. Also studied were the rates and mechanisms of NO “on” reactions with model water soluble heme compounds, the ferriheme protein met-myoglobin and various ruthenium complexes using ns laser flash photolysis techniques. An overview of these studies is presented.« less

  17. Complex metallic alloys as new materials for additive manufacturing

    PubMed Central

    Kenzari, Samuel; Bonina, David; Marie Dubois, Jean; Fournée, Vincent

    2014-01-01

    Additive manufacturing processes allow freeform fabrication of the physical representation of a three-dimensional computer-aided design (CAD) data model. This area has been expanding rapidly over the last 20 years. It includes several techniques such as selective laser sintering and stereolithography. The range of materials used today is quite restricted while there is a real demand for manufacturing lighter functional parts or parts with improved functional properties. In this article, we summarize recent work performed in this field, introducing new composite materials containing complex metallic alloys. These are mainly Al-based quasicrystalline alloys whose properties differ from those of conventional alloys. The use of these materials allows us to produce light-weight parts consisting of either metal–matrix composites or of polymer–matrix composites with improved properties. Functional parts using these alloys are now commercialized. PMID:27877661

  18. Electron spin resonance of radicals and metal complexes

    NASA Astrophysics Data System (ADS)

    The materials are a collection of extended synopsis of papers presented at the conference sessions. The broad area of magnetic technique applications has been described as well as their spectra interpretation methods. The ESR, NMR, ENDOR, and spin echo were applied for studying the radiation and UV induced radicals in chemical and biological systems. Also in the study of complexes of metallic ions (having the paramagnetic properties) and their interaction with the matrix, the magnetic techniques have been commonly used. They are also very convenient tool for the study of reaction kinetics and mechanism as well as interaction of paramagnetic species with themselves and crystal lattice or with the surface as for the catalytic processes.

  19. Acetohydroxamic Acid Complexes with Trivalent f-Block Metal Cations

    SciTech Connect

    Sinkov, Serguei I.; Choppin, Gregory

    2003-11-01

    Acetohydroxamic acid has been studied by optical absorbance spectroscopy as a complex forming reagent for the lighter trivalent lanthanides and actinides (Pu(III) and Am(III)) in aqueous solution at 2.0 M (NaClO4) ionic strength. The highest stoichiometry in all the cases studied has been found to be a 1:4 metal-to-ligand ratio; formation of tetrahydroxamato species requires a high excess of the ligand and alkaline pH, Spectrophotometric monitoring confirmed the presence of Pu(III) by electrochemical reduction of Pu(IV) in the course of the pH titration experiment. The formation constants can be used for optimization of processing flowsheets in the advanced PUREX process.

  20. Friction and solid-solid adhesion on complex metallic alloys

    PubMed Central

    Dubois, Jean-Marie; Belin-Ferré, Esther

    2014-01-01

    The discovery in 1987 of stable quasicrystals in the Al–Cu–Fe system was soon exploited to patent specific coatings that showed reduced friction in ambient air against hard antagonists. Henceforth, it was possible to develop a number of applications, potential or commercially exploited to date, that will be alluded to in this topical review. A deeper understanding of the characteristics of complex metallic alloys (CMAs) may explain why material made of metals like Al, Cu and Fe offers reduced friction; low solid–solid adhesion came later. It is linked to the surface energy being significantly lower on those materials, in which translational symmetry has become a weak property, that is determined by the depth of the pseudo-gap at the Fermi energy. As a result, friction is anisotropic in CMAs that builds up according to the translation symmetry along one direction, but is aperiodic along the other two directions. A review is given in this article of the most salient data found along these lines during the past two decades or so. PMID:27877675

  1. A Method of Springback Prediction and Tool Shape Compensation for Multi-curvature Sheet Metal Bending

    NASA Astrophysics Data System (ADS)

    Zhou, Chi; Liao, Juan; Zhu, Yin; Chen, Zhenjiao

    2010-06-01

    Advanced High Strength Steels (AHSS) are used increasingly in automobile structure parts to reduce the vehicle weight while keeping the safety standard. But their high values of the ratio of strength to Young's modulus cause more springback problems. A method of calculating the compensated tool shape for complex bending shapes is proposed in this paper. The method is composed of 3 steps: firstly the cross-section profile of a part was discretized into points and their corresponding curvatures; then an analytic algorithm based on plastic bending theory is applied to calculate the compensated curvatures of each point; finally, a numerical algorithm based on differential geometry is used to construct the tool shape according to the compensated curvatures of each point. A wave-shaped AHSS part with three different curvatures had been used to evaluate this method. The experimental results showed that the max curvature variance between the actual bending parts and desired shape is less than 4%, which is satisfying for most engineering applications.

  2. The Effect of Complex Formation upon the Redox Potentials of Metallic Ions. Cyclic Voltammetry Experiments.

    ERIC Educational Resources Information Center

    Ibanez, Jorge G.; And Others

    1988-01-01

    Describes experiments in which students prepare in situ soluble complexes of metal ions with different ligands and observe and estimate the change in formal potential that the ion undergoes upon complexation. Discusses student formation and analysis of soluble complexes of two different metal ions with the same ligand. (CW)

  3. Metal-metal interactions in linear tri-, penta-, hepta-, and nona-nuclear ruthenium string complexes.

    PubMed

    Niskanen, Mika; Hirva, Pipsa; Haukka, Matti

    2012-05-01

    Density functional theory (DFT) methodology was used to examine the structural properties of linear metal string complexes: [Ru(3)(dpa)(4)X(2)] (X = Cl(-), CN(-), NCS(-), dpa = dipyridylamine(-)), [Ru(5)(tpda)(4)Cl(2)], and hypothetical, not yet synthesized complexes [Ru(7)(tpta)(4)Cl(2)] and [Ru(9)(ppta)(4)Cl(2)] (tpda = tri-α-pyridyldiamine(2-), tpta = tetra-α-pyridyltriamine(3-), ppta = penta-α-pyridyltetraamine(4-)). Our specific focus was on the two longest structures and on comparison of the string complexes and unsupported ruthenium backboned chain complexes, which have weaker ruthenium-ruthenium interactions. The electronic structures were studied with the aid of visualized frontier molecular orbitals, and Bader's quantum theory of atoms in molecules (QTAIM) was used to study the interactions between ruthenium atoms. The electron density was found to be highest and distributed most evenly between the ruthenium atoms in the hypothetical [Ru(7)(tpta)(4)Cl(2)] and [Ru(9)(ppta)(4)Cl(2)] string complexes.

  4. Resonant Ultrasound Studies of Complex Transition Metal Oxides

    SciTech Connect

    Dr. Henry Bass; Dr. J. R. Gladden

    2008-08-18

    Department of Energy EPSCoR The University of Mississippi Award: DE-FG02-04ER46121 Resonant Ultrasound Spectroscopy Studies of Complex Transition Metal Oxides The central thrust of this DOE funded research program has been to apply resonant ultrasound spectroscopy (RUS), an elegant and efficient method for determining the elastic stiffness constants of a crystal, to the complex and poorly understood class of materials known as transition metal oxides (TMOs). Perhaps the most interesting and challenging feature of TMOs is their strongly correlated behavior in which spin, lattice, and charge degrees of freedom are strongly coupled. Elastic constants are a measure of the interatomic potentials in a crystal and are thus sensitive probes into the atomic environment. This sensitivity makes RUS an ideal tool to study the coupling of phase transition order parameters to lattice strains. The most significant result of the project has been the construction of a high temperature RUS apparatus capable of making elastic constant measurements at temperatures as high as 1000 degrees Celsius. We have designed and built novel acoustic transducers which can operate as high as 600 degrees Celsius based on lithium niobate piezoelectric elements. For measurement between 600 to 1000 C, a buffer rod system is used in which the samples under test and transducers are separated by a rod with low acoustic attenuation. The high temperature RUS system has been used to study the charge order (CO) transition in transition metal oxides for which we have discovered a new transition occurring about 35 C below the CO transition. While the CO transition exhibits a linear coupling between the strain and order parameter, this new precursor transition shows a different coupling indicating a fundamentally different mechanism. We have also begun a study, in collaboration with the Jet Propulsion Laboratory, to study novel thermoelectric materials at elevated temperatures. These materials include silicon

  5. Understanding atomistic phenomenon for hydrogen storage in complex metal hydrides

    NASA Astrophysics Data System (ADS)

    Chopra, Irinder Singh

    The storage of hydrogen into metals in the form of complex metal hydrides is one of the most promising methods. However, the incorporation and release of hydrogen requires very high temperatures. The discovery that the addition of Ti compounds lowers NaAlH4 decomposition barriers closer to ambient conditions, has re-ignited the field, and it is believed that surface processes are responsible for H2 dissociation and mass transport required to form the hydrogenated materials. Such surface reactions mechanisms are however difficult to study with typical spectroscopic and imaging surface science tools. Alanes lack contrast under electron microscopes and can modify the Scanning Tunneling Microscopy (STM) tips. Infrared spectroscopy would be a sensitive probe to investigate the adsorption of hydrogen providing, but has so far failed to detect chemisorbed hydrogen on Ti-doped Al surfaces due to the weak Al-H dynamic dipole moment. Thus despite extensive investigations, the fundamental mechanisms of the role of Ti and alane formation have remained elusive. In this study combining surface infrared (IR) spectroscopy and density functional theory (DFT), we provide atomistic details about the role of Ti as a catalyst for hydrogen uptake and alane formation and evolution on single crystal Al(111) and Al(100) surfaces. We are able to detect H indirectly by using CO as a probe molecule of the weak Al-H species. We demonstrate that aluminum doped with very small amounts of titanium (in a specific configuration) can activate molecular hydrogen at temperatures as low as 90K. Once dissociated, hydrogen spills over from these catalytic sites on to the Al surface and protects the surface from further reactions. We also show that, on Ti-doped Al surfaces, the diffusion dynamics are severely altered by Ti doping (Atomic hydrogen and AlH3 are trapped at the Ti sites) as indicated by a marked decrease of higher alane concentrations, which is deleterious for hydrogen storage for which mass

  6. Effects of humic acid-metal complexes on hepatic carnitine palmitoyltransferase, carnitine acetyltransferase and catalase activities

    SciTech Connect

    Fungjou Lu; Youngshin Chen . Dept. of Biochemistry); Tienshang Huang . Dept. of Medicine)

    1994-03-01

    A significant increase in activities of hepatic carnitine palmitoyltransferase and carnitine acetyltransferase was observed in male Balb/c mice intraperitoneally injected for 40 d with 0.125 mg/0.1 ml/d humic acid-metal complexes. Among these complexes, the humic acid-As complex was relatively effective, whereas humic acid-25 metal complex was more effective, and humic acid-26 metal complex was most effective. However, humic acid or metal mixtures, or metal such as As alone, was not effective. Humic acid-metal complexes also significantly decreased hepatic catalase activity. A marked decrease of 60-kDa polypeptide in liver cytoplasm was also observed on SDS-polyacrylamide gel electrophoresis after the mice had been injected with the complexes. Morphological analysis of a histopathological biopsy of such treated mice revealed several changes in hepatocytes, including focal necrosis and cell infiltration, mild fatty changes, reactive nuclei, and hypertrophy. Humic acid-metal complexes affect activities of metabolic enzymes of fatty acids, and this results in accumulation of hydrogen peroxide and increase of the lipid peroxidation. The products of lipid peroxidation may be responsible for liver damage and possible carcinogenesis. Previous studies in this laboratory had shown that humic acid-metal complex altered the coagulation system and that humic acid, per se, caused vasculopathy. Therefore, humic acid-metal complexes may be main causal factors of not only so-called blackfoot disease, but also the liver cancer prevailing on the southwestern coast of Taiwan.

  7. Metal complex-based electron-transfer mediators in dye-sensitized solar cells

    DOEpatents

    Elliott, C. Michael; Sapp, Shawn A.; Bignozzi, Carlo Alberto; Contado, Cristiano; Caramori, Stefano

    2006-03-28

    This present invention provides a metal-ligand complex and methods for using and preparing the same. In particular, the metal-ligand complex of the present invention is of the formula: L.sub.a-M-X.sub.b where L, M, X, a, and b are those define herein. The metal-ligand complexes of the present invention are useful in a variety of applications including as electron-transfer mediators in dye-sensitized solar cells and related photoelectrochromic devices.

  8. Water-in-Supercritical CO2 Microemulsion Stabilized by a Metal Complex.

    PubMed

    Luo, Tian; Zhang, Jianling; Tan, Xiuniang; Liu, Chengcheng; Wu, Tianbin; Li, Wei; Sang, Xinxin; Han, Buxing; Li, Zhihong; Mo, Guang; Xing, Xueqing; Wu, Zhonghua

    2016-10-17

    Herein we propose for the first time the utilization of a metal complex for forming water-in-supercritical CO2 (scCO2 ) microemulsions. The water solubility in the metal-complex-stabilized microemulsion is significantly improved compared with the conventional water-in-scCO2 microemulsions stabilized by hydrocarbons. Such a microemulsion provides a promising route for the in situ CO2 reduction catalyzed by a metal complex at the water/scCO2 interface.

  9. Group 4 Metalloporphyrin diolato Complexes and Catalytic Application of Metalloporphyrins and Related Transition Metal Complexes

    SciTech Connect

    Du, Guodong

    2003-01-01

    -, bis-alkoxo, and chelating diolato complexes, depending on the identity of diols and the stoichiometry employed. It was also found that tin porphyrin complexes promoted the oxidative cleavage of vicinal diols and the oxidation of α-ketols to α-diketones with dioxygen. In extending the chemistry of metalloporphyrins and analogous complexes, a series of chiral tetraaza macrocyclic ligands and metal complexes were designed and synthesized. Examination of iron(II) complexes showed that they were efficient catalysts for the cyclopropanation of styrene by diazo reagents. Good yields and high diastereoselectivity were obtained with modest enantioselectivity. A rationalization of the stereoselectivity was presented on the basis of structural factors in a carbene intermediate.

  10. Immobilizing Molecular Metal Dithiolene-Diamine Complexes on 2D Metal-Organic Frameworks for Electrocatalytic H2 Production.

    PubMed

    Dong, Renhao; Zheng, Zhikun; Tranca, Diana C; Zhang, Jian; Chandrasekhar, Naisa; Liu, Shaohua; Zhuang, Xiaodong; Seifert, Gotthard; Feng, Xinliang

    2017-02-16

    Carbon electrocatalysts consisting of metal complexes such as MNx or MSx are promising alternatives to high-cost Pt catalysts for the hydrogen evolution reaction (HER). However, the exact HER active sites remain elusive. Here, molecular metal dithiolene-diamine (MS2 N2 , M=Co and Ni), metal bis(dithiolene) (MS4 ), and metal bis(diamine) (MN4 ) complexes were selectively incorporated into carbon-rich 2D metal-organic frameworks (2D MOFs) as model carbon electrocatalysts. The 2D MOF single layers, powders, and composites with graphene were thus prepared and showed definite active sites for H2 generation. The electrocatalytic HER activity of the 2D MOF-based catalysts with different metal complexes follow the order of MS2 N2 >MN4 >MS4 . Moreover, the protonation preferentially occurred on the metal atoms, and the concomitant heterolytic elimination of H2 was favored on the M-N units in the MS2 N2 active centers. The results provide an in-depth understanding of the catalytic active sites, thus making way for the future development of metal complexes in carbon-rich electrode materials for energy generation.

  11. Membrane permeable luminescent metal complexes for cellular imaging

    NASA Astrophysics Data System (ADS)

    Neugebauer, Ute; Cosgrave, Lynda; Pellegrin, Yann; Devocelle, Marc; Forster, Robert J.; Keyes, Tia E.

    2012-06-01

    The spectroscopic and photophysical properties of ruthenium polypyridyl polypeptide conjugates of the type [Ru(bpy)2PIC-Argn]n+2+, where bpy is 2,2-bipyridyl (bpy), PIC is 2-(4-carboxyphenyl)imidazo[4,5- f][1,10]phenanthroline and PIC-Argn is this ligand peptide bonded to polyarginine where n is 5 or 8, is described. The resonance Raman spectroscopy of the peptide conjugated complex and parent are strongly pH dependent and demonstrate a switch of lowest energy charge transfer transition between bpy and pic ligands as s function of pH. The pKa of the imidazole ring on the complex is obtained from resonance Raman spectroscopy as 7.8 +/- 0.2. The luminescence lifetime of the complex is strongly oxygen dependent and a Stern-Volmer plot of O2 quenching for [Ru(bpy)2(PIC-Arg8)]10+ yielded a KSV value of 2300 +/- 420 M-1 which was independent of pH over the range 2 to 11. The complexes, because of their large Stokes shifts can, uniquely, be used under identical conditions of probe concentration and excitation wavelength for resonance Raman and luminescence cellular imaging. Cellular imaging was conducted using SP2 myeloma cells which confirmed that the [Ru(bpy)2(PIC-Arg8)]10+ is readily taken up by mammalian cells although the parent and pentarginine analogues are not membrane permeable. Preliminary examples of multi-parameter imaging using these probes were presented. Resonance Raman maps of [Ru(bpy)2(PIC-Arg8)]10+ within living myeloma cells showed on the basis of spectral discrimination, attributed to pH, three distinct regions of the cell could be identified, ascribed to the nucleus, the cytoplasm and the membranes. Luminescence lifetime imaging showed quite large variations in the probe lifetime within the living cell which was tentatively ascribed to variation in O2 concentration about the cell. Preliminary estimates of O2 concentration were made and it was found that the membranes, both inner and outer are the most O2 rich regions of the cell. Overall, we propose

  12. From metallic gold to [Au(NHC)2](+) complexes: an easy, one-pot method.

    PubMed

    Lozada-Rodríguez, Leticia; Pelayo-Vázquez, José B; Rangel-Salas, Irma I; Alvarado-Rodríguez, José G; Peregrina-Lucano, A Aarón; Pérez-Centeno, Armando; López-Dellamary-Toral, Fernando A; Cortes-Llamas, Sara A

    2017-03-21

    A simple and direct method is described to prepare cationic bis(NHC)-Au(i) complexes containing N-alkyl or N-aryl NHC ligands to generate relevant gold complexes using metallic gold as the starting material.

  13. Thin films of metal oxides grown by chemical vapor deposition from volatile transition metal and lanthanide metal complexes

    NASA Astrophysics Data System (ADS)

    Pollard, Kimberly Dona

    1998-08-01

    This thesis describes the synthesis and characterization of novel volatile metal-organic complexes for the chemical vapor deposition (CVD) of metal oxides. Monomeric tantalum complexes, lbrack Ta(OEt)sb4(beta-diketonate)) are prepared by the acid-base reaction of lbrack Tasb2(OEt)sb{10}rbrack with a beta-diketone, (RC(O)CHsb2C(O)Rsp' for R = CHsb3, Rsp' = CFsb3; R = Rsp'=C(CHsb3)sb3; R = Csb3Fsb7,\\ Rsp'=C(CHsb3)sb3;\\ R=Rsp'=CFsb3; and R = Rsp' = CHsb3). The products are characterized spectroscopically. Thermal CVD using these complexes as precursors gave good quality Tasb2Osb5 thin films which are characterized by XPS, SEM, electrical measurements, and XRD. Factors affecting the film deposition such as the type of carrier gas and the temperature of the substrate were considered. Catalyst-enhanced CVD reactions with each of the precursors and a palladium catalyst, ((2-methylallyl)Pd(acac)), were studied as a lower temperature route to good quality Tasb2Osb5 films. The decomposition mechanism at the hot substrate surface was studied. Precursors for the formation of yttria by CVD were examined. New complexes of the form (Y(hfac)sb3(glyme)), (hfac = \\{CFsb3C(O)CHC(O)CFsb3\\}sp-,\\ glyme=CHsb3O(CHsb2CHsb2O)sb{n}CHsb3 for n = 1-4) were synthesized and characterized spectroscopically. X-ray structural determinations of three new complexes were obtained. CVD reaction conditions were determined which give YOF films and, with catalyst-enhanced CVD, reaction conditions which give selective formation of Ysb2Osb3, YOF, or YFsb3. The films were studied by XPS, SEM, and XRD. Decomposition mechanisms which lead to film formation, together with a possible route for fluorine atom transfer from the ligand to the metal resulting in fluorine incorporation, were studied by analysis of exhaust products using GC-MS. Novel precursors of the form lbrack Ce(hfac)sb3(glyme)rbrack,\\ (hfac=\\{CFsb3C(O)CHC(O)CFsb3\\}sp-,\\ glyme=CHsb3O(CHsb2CHsb2O)sb{n}CHsb3, n = 1-4) for CVD of ceria were

  14. A Fenton-like oxidation process using corrosion of iron metal sheet surfaces in the presence of hydrogen peroxide: a batch process study using model pollutants.

    PubMed

    Namkung, K C; Burgess, A E; Bremner, D H

    2005-03-01

    This study evaluates a new method for chemically destroying organic pollutants in wastewater using spontaneous corrosion of iron metal sheet surfaces in the presence of hydrogen peroxide. Model pollutants (phenol and benzoic acid) were degraded in batch experiments to investigate which parameters affected the process performance. Iron metal sheet surfaces spontaneously corrode under acidic conditions producing iron species (mainly ferrous ions) dissolved in aqueous solution, which react with hydrogen peroxide via the Fenton reaction. In order to optimise the oxidation system, several factors (pH, H2O2 dosage, initial concentration of organic substances) affecting corrosion of the iron metal sheet surface were investigated. Total iron concentration in solution was investigated with different dosages of H2O2 (100 mg l(-1), 1000 mg l(-1) and 1900 mg l(-1)) at different pH values (1.5, 2.5 and 3.0). Iron corrosion increased with the decrease of pH. The addition of H2O2 resulted in a significant increase of iron corrosion. Organic substances also had a marked effect with, for instance, the presence of phenol or benzoic acid resulting in a considerable increase of iron corrosion. In contrast, the absence of either hydrogen peroxide or iron metal brought no change in total organic carbon (TOC). In order to obtain the most effective combination of parameters for TOC removal of phenol solution, experiments were conducted under varied conditions. The experimental results showed that there is an optimum pH requirement (in this work, 2.5). The factors affecting the TOC removal are discussed and the oxidation mechanisms leading to mineralization of organic substances are proposed.

  15. Metals fact sheet - Dysprosium

    SciTech Connect

    1997-01-01

    The article contains a summary of factors pertinent to dysprosium use. Geology and exploitation, mineral sources, production processes, global production,applications, and the dysprosium market are reviewed. Applications very briefly described include use as a cooling agent in nuclear control rods, magnets, magnetostrictive devices, phosphors, photoelectric devices, and glass. Current and historical market prices are given.

  16. Metals Fact Sheet: Neodymium

    SciTech Connect

    1992-11-01

    Neodymium was discovered in 1898 when it was separated from {open_quotes}dydimium,{close_quotes} a praseodymium-neodymium compound that was thought to be only one element. {open_quotes}Neodymium{close_quotes} is derived from the Greek words {open_quotes}neos{close_quotes} and {open_quotes}didymos,{close_quotes} which translates to {open_quotes}new twin.{close_quotes} This article discusses sources and applications of the element, and reviews world reserves and demands. Price trends in the commodity are also noted.

  17. Capillary electrophoresis application in metal speciation and complexation characterization

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Capillary electrophoresis is amenable to the separation of metal ionic species and the characterization of metal-ligand interactions. This book chapter reviews and discusses three representative case studies in applications of CE technology in speciation and reactions of metal with organic molecules...

  18. Thermal properties of metal-metal bonded Pd(I) complexes supported onto porous Vycor glass.

    PubMed

    Gimenez, Iara F; Alves, Oswaldo L

    2008-06-01

    Thermal behavior of the complexes Pd2(dppm)2Cl2, Pd2(dppm)2(SnCl3)Cl and Pd2(dppm)2(SnCl3)2 (dppm=bis[diphenylphosphino(methane)], ((C6H5)2PCH2P(C6H5)2) in the solid state and immobilized onto porous Vycor glass was studied. Similar decomposition mechanisms were observed for the solid and immobilized complexes, with a small thermal stabilization upon immobilization. The decomposition products were characterized by X-ray diffractometry, Raman and diffuse reflectance infrared spectroscopy, which indicated the presence of a mixture of metallic palladium and oxidized species such as PdO,condensed phosphates, SnO2 and SnP2O7. According to X-ray diffractometry, the decomposition products of the immobilized complexes presented higher amounts of PdO than the solid-state residues, probably as an effect of interactions with silanol groups present in the glass surface.

  19. Cutting Guide for Fibrous Sheets

    NASA Technical Reports Server (NTRS)

    Warren, A., D.

    1985-01-01

    Tool facilitates repetitive cutting of fibrous sheets. Flexible aluminum tape allows metal strips folded back on themselves, exposing fresh material for cutting. More than one strip folded back, and cutting width therefore increased in multiples of strip width. Developed for cutting strips of alumina-fiber matting, tool also used on such materials as felts, textiles, and sheet metals.

  20. Chirp-driven vibrational distribution in transition metal carbonyl complexes.

    PubMed

    Gollub, C; Korff, B M R; Kompa, K L; de Vivie-Riedle, R

    2007-01-21

    In this theoretical study vibrational ladder climbing in transition metal carbonyl complexes, as a possible means to initialize chemical ground state reactions, and the resulting vibrational population distribution using chirped mid-infrared femtosecond laser pulses is investigated. Our model system is MnBr(CO)(5), a strong IR-absorber within an experimentally easily accessible wavelength region. Special emphasis is put on the perturbation due to additional vibrational modes, especially on one, which allows dissociation at low energies. The related potential energy surface for the three representative modes is calculated, whereon quantum dynamics calculations, including the laser-molecule interaction, are performed. No significant coupling could be detected, neither in the bound, nor in the dissociative region. Contrarily, we found a dynamical barrier even for energies high above the dissociation limit. Different vibrational population distributions after the laser excitation of the CO stretching mode could be generated in dependence of the chirp parameters. Based on these findings we simulated the laser excitation corresponding to an experiment by M. Joffre et al., Proc. Natl. Acad. Ssi. U. S. A., 2004, 101(36), 13216-13220, where coherent vibrational ladder climbing in carboxyhemoglobin was demonstrated and we could offer an explanation for an open question, concerning the interpretation of the spectroscopic data.

  1. The build-up, configuration, and dynamical sensitivity of the Eurasian ice-sheet complex to Late Weichselian climatic and oceanic forcing

    NASA Astrophysics Data System (ADS)

    Patton, Henry; Hubbard, Alun; Andreassen, Karin; Winsborrow, Monica; Stroeven, Arjen P.

    2016-12-01

    The Eurasian ice-sheet complex (EISC) was the third largest ice mass during the Last Glacial Maximum (LGM), after the Antarctic and North American ice sheets. Despite its global significance, a comprehensive account of its evolution from independent nucleation centres to its maximum extent is conspicuously lacking. Here, a first-order, thermomechanical model, robustly constrained by empirical evidence, is used to investigate the dynamics of the EISC throughout its build-up to its maximum configuration. The ice flow model is coupled to a reference climate and applied at 10 km spatial resolution across a domain that includes the three main spreading centres of the Celtic, Fennoscandian and Barents Sea ice sheets. The model is forced with the NGRIP palaeo-isotope curve from 37 ka BP onwards and model skill is assessed against collated flowsets, marginal moraines, exposure ages and relative sea-level history. The evolution of the EISC to its LGM configuration was complex and asynchronous; the western, maritime margins of the Fennoscandian and Celtic ice sheets responded rapidly and advanced across their continental shelves by 29 ka BP, yet the maximum aerial extent (5.48 × 106 km2) and volume (7.18 × 106 km3) of the ice complex was attained some 6 ka later at c. 22.7 ka BP. This maximum stand was short-lived as the North Sea and Atlantic margins were already in retreat whilst eastern margins were still advancing up until c. 20 ka BP. High rates of basal erosion are modelled beneath ice streams and outlet glaciers draining the Celtic and Fennoscandian ice sheets with extensive preservation elsewhere due to frozen subglacial conditions, including much of the Barents and Kara seas. Here, and elsewhere across the Norwegian shelf and North Sea, high pressure subglacial conditions would have promoted localised gas hydrate formation.

  2. Studies on Oligomer Metal Complexes Derived from Bisamic Acid of Pyromellitic Dianhydride and 4-Bromoaniline

    PubMed Central

    Patel, Yogesh S.

    2014-01-01

    Novel oligomer metal complexes (2a–f) of the ligand 2,5-bis((4-bromophenyl)carbamoyl) terephthalic acid (1) were prepared using transition metal salts and characterized by various spectroscopic techniques. The geometry of oligomer metal complexes was carried out by electronic spectral analysis and magnetic measurement studies. Polymeric properties have also been carried out. Ligand was synthesized using pyromellitic dianhydride and 4-bromoaniline. It was duly characterized. All novel synthesized compounds 1 and 2a–f were evaluated for their antibacterial and antifungal activity. The results showed significantly higher antibacterial and antifungal activity of oligomer metal complexes compared to the ligand. PMID:27379295

  3. Studies on Oligomer Metal Complexes Derived from Bisamic Acid of Pyromellitic Dianhydride and 4-Bromoaniline.

    PubMed

    Patel, Yogesh S

    2014-01-01

    Novel oligomer metal complexes (2a-f) of the ligand 2,5-bis((4-bromophenyl)carbamoyl) terephthalic acid (1) were prepared using transition metal salts and characterized by various spectroscopic techniques. The geometry of oligomer metal complexes was carried out by electronic spectral analysis and magnetic measurement studies. Polymeric properties have also been carried out. Ligand was synthesized using pyromellitic dianhydride and 4-bromoaniline. It was duly characterized. All novel synthesized compounds 1 and 2a-f were evaluated for their antibacterial and antifungal activity. The results showed significantly higher antibacterial and antifungal activity of oligomer metal complexes compared to the ligand.

  4. Superconductors and Complex Transition Metal Oxides for Tunable THz Plasmonic Metamaterials

    SciTech Connect

    Singh, Ranjan; Xiong, Jie; Azad, Md A.; Yang, Hao; Trugman, Stuart A.; Jia, Quanxi; Taylor, Antoinette; Chen, Houtong

    2012-07-13

    The outline of this presentation are: (1) Motivation - Non-tunability of metal metamaterials; (2) Superconductors for temperature tunable metamaterials; (3) Ultrafast optical switching in superconductor metamaterials; (4) Controlling the conductivity with infrared pump beam; (5) Complex metal oxides as active substrates - Strontium Titanate; and (6) Conclusion. Conclusions are: (1) High Tc superconductors good for tunable and ultrafast metamaterials; (2) Large frequency and amplitude tunability in ultrathin superconductor films; (3) Such tunable properties cannot be accessed using metals; (4) Complex metal oxides can be used as active substrates - large tunability; (5) Complex oxides fail to address the issue of radiation losses in THz metamaterials.

  5. Solid State Pathways to Complex Shape Evolution and Tunable Porosity during Metallic Crystal Growth

    PubMed Central

    Valenzuela, Carlos Díaz; Carriedo, Gabino A.; Valenzuela, María L.; Zúñiga, Luis; O'Dwyer, Colm

    2013-01-01

    Growing complex metallic crystals, supported high index facet nanocrystal composites and tunable porosity metals, and exploiting factors that influence shape and morphology is crucial in many exciting developments in chemistry, catalysis, biotechnology and nanoscience. Assembly, organization and ordered crystallization of nanostructures into complex shapes requires understanding of the building blocks and their association, and this relationship can define the many physical properties of crystals and their assemblies. Understanding crystal evolution pathways is required for controlled deposition onto surfaces. Here, complex metallic crystals on the nano- and microscale, carbon supported nanoparticles, and spinodal porous noble metals with defined inter-feature distances in 3D, are accomplished in the solid-state for Au, Ag, Pd, and Re. Bottom-up growth and positioning is possible through competitive coarsening of mobile nanoparticles and their site-specific crystallization in a nucleation-dewetted matrix. Shape evolution, density and growth mechanism of complex metallic crystals and porous metals can be imaged during growth. PMID:24026532

  6. 40 CFR 721.4680 - Metal salts of complex inorganic oxyacids (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Metal salts of complex inorganic... AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.4680 Metal salts of complex inorganic...

  7. Assigning Oxidation States to Some Metal Dioxygen Complexes of Biological Interest.

    ERIC Educational Resources Information Center

    Summerville, David A.; And Others

    1979-01-01

    The bonding of dioxygen in metal-dioxygen complexes is discussed, paying particular attention to the problems encountered in assigning conventional oxidation numbers to both the metal center and coordinated dioxygen. Complexes of iron, cobalt, chromium, and manganese are considered. (BB)

  8. 40 CFR Appendix B to Part 414 - Complexed Metal-Bearing Waste Streams

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 29 2014-07-01 2012-07-01 true Complexed Metal-Bearing Waste Streams B Appendix B to Part 414 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT... 414—Complexed Metal-Bearing Waste Streams Chromium Azo dye intermediates/Substituted diazonium...

  9. 40 CFR Appendix B to Part 414 - Complexed Metal-Bearing Waste Streams

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 28 2010-07-01 2010-07-01 true Complexed Metal-Bearing Waste Streams B Appendix B to Part 414 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT... 414—Complexed Metal-Bearing Waste Streams Chromium Azo dye intermediates/Substituted diazonium...

  10. 40 CFR Appendix B to Part 414 - Complexed Metal-Bearing Waste Streams

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 30 2012-07-01 2012-07-01 false Complexed Metal-Bearing Waste Streams B Appendix B to Part 414 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Appendix B to Part 414—Complexed Metal-Bearing Waste Streams Chromium Azo dye...

  11. 40 CFR Appendix B to Part 414 - Complexed Metal-Bearing Waste Streams

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 29 2011-07-01 2009-07-01 true Complexed Metal-Bearing Waste Streams B Appendix B to Part 414 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT... 414—Complexed Metal-Bearing Waste Streams Chromium Azo dye intermediates/Substituted diazonium...

  12. 40 CFR Appendix B to Part 414 - Complexed Metal-Bearing Waste Streams

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 30 2013-07-01 2012-07-01 true Complexed Metal-Bearing Waste Streams B Appendix B to Part 414 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT... 414—Complexed Metal-Bearing Waste Streams Chromium Azo dye intermediates/Substituted diazonium...

  13. VCD spectroscopy as an excellent probe of chiral metal complexes containing a carbon monoxide vibrational chromophore.

    PubMed

    Fusè, Marco; Mazzeo, Giuseppe; Longhi, Giovanna; Abbate, Sergio; Zerla, Daniele; Rimoldi, Isabella; Contini, Alessandro; Cesarotti, Edoardo

    2015-06-07

    Vibrational circular dichroism, VCD, gives evidence that the carbon monoxide chromophore in a heteroleptic cyclopentadienyl Ru(ii)-carbonyl complex is very sensitive to the chirality of the metal centre and becomes an excellent probe to define the configuration of chiral metal complexes.

  14. Complex transition metal hydrides: linear correlation of countercation electronegativity versus T-D bond lengths.

    PubMed

    Humphries, T D; Sheppard, D A; Buckley, C E

    2015-06-30

    For homoleptic 18-electron complex hydrides, an inverse linear correlation has been established between the T-deuterium bond length (T = Fe, Co, Ni) and the average electronegativity of the metal countercations. This relationship can be further employed towards aiding structural solutions and predicting physical properties of novel complex transition metal hydrides.

  15. Site-selective hydrolysis of tRNA by lanthanide metal complexes

    SciTech Connect

    Hayashi, Nobuhiro ); Takeda, Naoya; Yashiro, Morio; Watanabe, Kimitsuna; Komiyama, Makoto ); Shiiba, Tetsuro )

    1993-12-22

    tRNA[sup Phe] is site-selectively hydrolyzed by lanthanide metal complexes (Ce(III), Eu(III), La(III)) of hexaimine macrocyclic ligands. The selectivities of the complexes are much higher than those of the metal ions and are strongly dependent on the ligand structure. The tertiary structure of tRNA is essential for the site-selective scission.

  16. Infrared Spectroscopic Analysis of Linkage Isomerism in Metal-Thiocyanate Complexes

    ERIC Educational Resources Information Center

    Baer, Carl; Pike, Jay

    2010-01-01

    We developed an experiment suitable for an advanced inorganic chemistry laboratory that utilizes a cooperative learning environment, which allows students to develop an empirical method of determining the bonding mode of a series of unknown metal-thiocyanate complexes. Students synthesize the metal-thiocyanate complexes and obtain the FT-IR…

  17. Novel Route to Transition Metal Isothiocyanate Complexes Using Metal Powders and Thiourea

    NASA Technical Reports Server (NTRS)

    Harris, Jerry D.; Eckles, William E.; Hepp, Aloysius F.; Duraj, Stan A.; Hehemann, David G.; Fanwick, Phillip E.; Richardson, John

    2003-01-01

    A new synthetic route to isothiocyanate-containing materials is presented. Eight isothiocyanate- 4-methylpyridine (y-picoline) compounds were prepared by refluxing metal powders (Mn, Fe, Co, Ni, and Cu) with thiourea in y-picoline. With the exception of compound 5,prepared with Co, the isothiocyanate ligand was generated in situ by the isomerization of thiourea to NH4+SCN- at reflux temperatures. The complexes were characterized by x-ray crystallography. Compounds 1,2, and 8 are the first isothiocyanate- 4-methylpyridine anionic compounds ever prepared and structurally characterized. Compounds 1 and 2 are isostructural with four equatorially bound isothiocyanate ligands and two axially bound y-picoline molecules. Compound 8 is a five-coordinate copper(II) molecule with a distorted square-pyramidal geometry. Coordinated picoline and two isothiocyanates form the basal plane and the remaining isothiocyanate is bound at the apex. Structural data are presented for all compounds.

  18. Heterobimetallic coordination polymers involving 3d metal complexes and heavier transition metals cyanometallates

    SciTech Connect

    Peresypkina, Eugenia V.; Samsonenko, Denis G.; Vostrikova, Kira E.

    2015-04-15

    The results of the first steps in the design of coordination polymers based on penta- and heptacyanometallates of heavier d transitions metals are presented. The 2D structure of the coordination polymers: [(Mn(acacen)){sub 2}Ru(NO)(CN){sub 5}]{sub n} and two complexes composed of different cyanorhenates, [Ni(cyclam)]{sub 2}[ReO(OH)(CN){sub 4}](ClO{sub 4}){sub 2}(H{sub 2}O){sub 1.25} and [Cu(cyclam)]{sub 2}[Re(CN){sub 7}](H{sub 2}O){sub 12}, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} (M=Ni, Cu) polymers does not allow to define strictly their dimensionality and to model anisotropic magnetic behavior of the compounds. However, with high probability a honey-comb like layer structure could be expected for [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} complexes, studied in this work, because such an arrangement is the most common among the bimetallic assemblies of hexa- and octacyanometallates with a ratio [M(cyclam)]/[M(CN){sub n}]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu{sub 4}N){sub 2}[Ru(NO)(CN){sub 5}], soluble in organic media. - Graphical abstract: The very first results in the design of 2D coordination polymers based on penta- and heptacyanometallates of 4d and5d transitions metals are presented. - Highlights: • Design of coordination polymers based on penta- and heptacyanometallates. • New Ru and Re cyanide based heterobimetallic coordination complexes. • Hydrolysis and ox/red processes involving [Re(CN){sub 7}]{sup 3+} during crystallization. • High magnetic anisotropy of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2}(H{sub 2}O){sub n}, M=Cu, Ni, complexes.

  19. Preparation, Physicochemical Characterization and Biological Evaluation of some Hesperidin Metal Complexes

    PubMed Central

    Daoud, Safa; Afifi, Fatma U; Al-Bakri, Amal G; Kasabri, Violet; Hamdan, Imad I

    2014-01-01

    The ability of hesperidin (HP) to form complexes with five metals; cobalt, nickel, zinc, calcium and magnesium was investigated. The complexation was studied using U.V spectroscopic titration, in methanol as well as aqueous buffer solutions (physiological conditions). Potential complexes were studied by IR and NMR spectroscopy, melting point and their solubility were also evaluated. The interaction of HP and its metal complexes with DNA was investigated by U.V spectroscopy. HP and its potential complexes were also tested for their ability to inhibit alpha amylase and alpha glucosidase enzymes. The results indicated that HP can form 1:1 complexes with cobalt, nickel and zinc in methanolic solution but not in aqueous buffers. Both HP and its metal complexes were found to intercalate DNA, at physiological condition, with preference to GC rich sequences. HP-metal complexes appeared to have higher affinity towards poly A DNA than the free HP. Neither HP nor its complexes exhibited antimicrobial activity against Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa or Candida albicans. Results showed that HP has little inhibitory action on glucosidase and amylase enzymes with no obvious effect of complexation on the behavior of free HP. In conclusion HP was shown to form 1:complexes with the studied metal in methanol but not in aqueous buffer solutions. In presence of DNA however, complex formation in aqueous solutions seem to be encouraged with differential effect between the complexes and free HP. PMID:25276191

  20. Transition Metal d-Orbital Splitting Diagrams: An Updated Educational Resource for Square Planar Transition Metal Complexes

    ERIC Educational Resources Information Center

    Bo¨rgel, Jonas; Campbell, Michael G.; Ritter, Tobias

    2016-01-01

    The presentation of d-orbital splitting diagrams for square planar transition metal complexes in textbooks and educational materials is often inconsistent and therefore confusing for students. Here we provide a concise summary of the key features of orbital splitting diagrams for square planar complexes, which we propose may be used as an updated…

  1. Electronic interactions in metal complexed photoconducting polymers : a ZINDO study.

    SciTech Connect

    Manas, E. S.; Chen, L. X.; Chemistry; Univ. of Pennsylvania School of Medicine

    2000-12-01

    Semi-empirical (INDO/s) calculations have been conducted on molecular fragments with zero to three phenylenevinylene (PV) units attached to 4 and 4{prime} positions of a 2,2{prime}-bipyridine (bpy) group, with and without chelated metal ions, mimicking metal-free and metal-chelated photoconducting polymers 1 and 2 [Chen et al., J. Phys. Chem. B 104 (2000) 1950]. The calculations suggest that: (1) a global lowering of the molecular orbital energy levels due to metal-chelation is responsible for the observed red-shift in the lowest energy transitions; and (2) metal chelation attenuates {pi}-electron delocalization. The relevance of these effects to photoluminescence of metal-chelated polymers is also discussed.

  2. Ultrasonic Additive Manufacturing: Weld Optimization for Aluminum 6061, Development of Scarf Joints for Aluminum Sheet Metal, and Joining of High Strength Metals

    NASA Astrophysics Data System (ADS)

    Wolcott, Paul J.

    Ultrasonic additive manufacturing (UAM) is a low temperature, solid-state manufacturing process that enables the creation of layered, solid metal structures with designed anisotropies and embedded materials. As a low temperature process, UAM enables the creation of active composites containing smart materials, components with embedded sensors, thermal management devices, and many others. The focus of this work is on the improvement and characterization of UAM aluminum structures, advancing the capabilities of ultrasonic joining into sheet geometries, and examination of dissimilar material joints using the technology. Optimized process parameters for Al 6061 were identified via a design of experiments study indicating a weld amplitude of 32.8 synum and a weld speed of 200 in/min as optimal. Weld force and temperature were not significant within the levels studied. A methodology of creating large scale builds is proposed, including a prescribed random stacking sequence and overlap of 0.0035 in. (0.0889 mm) for foils to minimize voids and maximize mechanical strength. Utilization of heat treatments is shown to significantly increase mechanical properties of UAM builds, within 90% of bulk material. The applied loads during the UAM process were investigated to determine the stress fields and plastic deformation induced during the process. Modeling of the contact mechanics via Hertzian contact equations shows that significant stress is applied via sonotrode contact in the process. Contact modeling using finite element analysis (FEA), including plasticity, indicates that 5000 N normal loads result in plastic deformation in bulk aluminum foil, while at 3000 N no plastic deformation occurs. FEA studies on the applied loads during the process, specifically a 3000 N normal force and 2000 N shear force, show that high stresses and plastic deformation occur at the edges of a welded foil, and base of the UAM build. Microstructural investigations of heat treated foils confirms

  3. Experimental investigation of the effect of the material damage induced in sheet metal forming process on the service performance of 22MnB5 steel

    NASA Astrophysics Data System (ADS)

    Zhuang, Weimin; Xie, Dongxuan; Chen, Yanhong

    2016-07-01

    The use of ultra-high strength steels through sheet metal forming process offers a practical solution to the lightweight design of vehicles. However, sheet metal forming process not only produces desirable changes in material properties but also causes material damage that may adversely influence the service performance of the material formed. Thus, an investigation is conducted to experimentally quantify such influence for a commonly used steel (the 22MnB5 steel) based on the hot and cold forming processes. For each process, a number of samples are used to conduct a uniaxial tensile test to simulate the forming process. After that, some of the samples are trimmed into a standard shape and then uniaxially extended until fracture to simulate the service stage. Finally, a microstructure test is conducted to analyze the microdefects of the remaining samples. Based on the results of the first two tests, the effect of material damage on the service performance of 22MnB5 steel is analyzed. It is found that the material damages of both the hot and cold forming processes cause reductions in the service performance, such as the failure strain, the ultimate stress, the capacity of energy absorption and the ratio of residual strain. The reductions are generally lower and non-linear in the former process but higher and linear in the latter process. Additionally, it is found from the microstructure analysis that the difference in the reductions of the service performance of 22MnB5 by the two forming processes is driven by the difference in the micro damage mechanisms of the two processes. The findings of this research provide a useful reference in terms of the selection of sheet metal forming processes and the determination of forming parameters for 22MnB5.

  4. [Studies on the interaction of the metal complex of hydrazide of podophyllic acid with DNA].

    PubMed

    Wang, Ping-Hong; Zhang, Qi; Wang, Liu-Fang; Song, Yu-Min; Qu, Jian-Qiang; Liu, Ying-Qian

    2006-05-01

    The interaction between the metal complex of hydrazide of podophyllic acid and calf thymus (CT) DNA was studied by using absorption spectra, fluorescence spectra and DNA heat denaturation. It was found that the intensity of the maximal absorption peaks from absorption spectra is weakened in the presence of the metal complex of hydrazide of podophyllic acid compared with that in the absence of the metal complex. All the experimental results show that the intercalation mode was proved to exist between HDPP-Ni complexes and CT DNA.

  5. Tetracyclines metal complexation: Significance and fate of mutual existence in the environment.

    PubMed

    Pulicharla, Rama; Hegde, Krishnamoorthy; Brar, Satinder Kaur; Surampalli, Rao Y

    2017-02-01

    Concern over tetracyclines (TCs) complexation with metals in the environment is growing as a new class of emerging contaminants. TCs exist as a different net charged species depending on their dissociation constants, pH and the surrounding environment. One of the key concerns about TCs is its strong tendency to interact with various metal ions and form metal complexes. Moreover, co-existence of TCs and metals in the environment and their interactions has shown increased antibiotic resistance. Despite extensive research on TCs complexation, investigations on their antibiotic efficiency and pharmacological profile in bacteria have been limited. In addition, the current knowledge on TCs metal complexation, their fate and risk assessment in the environment are inadequate to obtain a clear understanding of their consequences on living systems. This indicates that vital and comprehensive studies on TCs-metal complexation, especially towards growing antibiotic resistance trends are required. This review summarizes the role of TCs metal complexation on the development of antibiotic resistance. Furthermore, impact of metal complexation on degradation, toxicity and the fate of TCs in the environment are discussed and future recommendations have been made.

  6. Behavior of Ti-5Al-2.5Sn ELI titanium alloy sheet parent and weld metal in the presence of cracks at 20 K

    NASA Technical Reports Server (NTRS)

    Sullivan, T. L.

    1971-01-01

    Through- and surface-cracked specimens of two thicknesses were tested in uniaxial tension. Surface-cracked specimens were generally found to be stronger than through-cracked specimens with the same crack length. Apparent surface-crack fracture toughness calculated using the Anderson modified Irwin equation remained relatively constant for cracks as deep as 90 percent of the sheet thickness. Subcritical growth of surface cracks was investigated. Comparison of chamber and open air welds showed chamber welds to be slightly tougher. Both methods produced welds with toughness that compared favorably with that of the parent metal. Weld efficiencies were above 94 percent.

  7. Synthesis, spectral studies and biological evaluation of 2-aminonicotinic acid metal complexes

    NASA Astrophysics Data System (ADS)

    Nawaz, Muhammad; Abbasi, Muhammad Waseem; Hisaindee, Soleiman; Zaki, Muhammad Javed; Abbas, Hira Fatima; Mengting, Hu; Ahmed, M. Arif

    2016-05-01

    We synthesized 2-aminonicotinic acid (2-ANA) complexes with metals such as Co(II), Fe(III), Ni(II), Mn(II), Zn(II), Ag(I),Cr(III), Cd(II) and Cu(II) in aqueous media. The complexes were characterized and elucidated using FT-IR, UV-Vis, a fluorescence spectrophotometer and thermo gravimetric analysis (TGA). TGA data showed that the stoichiometry of complexes was 1:2 metal/ligand except for Ag(I) and Mn(II) where the ratio was 1:1. The metal complexes showed varied antibacterial, fungicidal and nematicidal activities. The silver and zinc complexes showed highest activity against Bacillus subtilis and Bacillus licheniformis respectively. Fusarium oxysporum was highly susceptible to nickel and copper complexes whereas Macrophomina phaseolina was completely inert to the complexes. The silver and cadmium complexes were effective against the root-knot nematode Meloidogyne javanica.

  8. Identification of metal species by ESI-MS/MS through release of free metals from the corresponding metal-ligand complexes

    PubMed Central

    Tsednee, Munkhtsetseg; Huang, Yu-Chen; Chen, Yet-Ran; Yeh, Kuo-Chen

    2016-01-01

    Electrospray ionization-mass spectrometry (ESI-MS) is used to analyze metal species in a variety of samples. Here, we describe an application for identifying metal species by tandem mass spectrometry (ESI-MS/MS) with the release of free metals from the corresponding metal–ligand complexes. The MS/MS data were used to elucidate the possible fragmentation pathways of different metal–deoxymugineic acid (–DMA) and metal–nicotianamine (–NA) complexes and select the product ions with highest abundance that may be useful for quantitative multiple reaction monitoring. This method can be used for identifying different metal–ligand complexes, especially for metal species whose mass spectra peaks are clustered close together. Different metal–DMA/NA complexes were simultaneously identified under different physiological pH conditions with this method. We further demonstrated the application of the technique for different plant samples and with different MS instruments. PMID:27240899

  9. Diagenesis of Metals Chemically Complexed to Bacteria: Laboratory Formation of Metal Phosphates, Sulfides, and Organic Condensates in Artificial Sediments

    PubMed Central

    Beveridge, T. J.; Meloche, J. D.; Fyfe, W. S.; Murray, R. G. E.

    1983-01-01

    Cells of Bacillus subtilis, when suspended in a 5mM metal solution, bind metals tenaciously to their cell walls. These metal-loaded cells, when mixed with a synthetic sediment and put under laboratory conditions to simulate low-temperature sediment diagenesis, nucleate the formation of a mixed assemblage of crystalline metal phosphates, metal sulfides, and polymeric, metal-complexed, organic residues. The sequential series of diagenetic events leading to the formation of authigenic mineral phases was followed by transmission electron microscopy and energy-dispersive X-ray analysis. The minerals quartz (SiO2) and calcite (CaCO3) were employed in the synthetic sediment. Crystalline magnetite (Fe2O3) and elemental sulfur were added as redox buffering agents to ensure anoxic conditions. Quartz and magnetite appeared unreactive throughout the experimental conditions. Elemental sulfur interacted with the metal-loaded cells, affected both the eventual chemistry and crystal habit of the metal phosphates, and formed a variety of crystalline metal sulfides. Calcite raised the pH of the fluid phase of the sediment, which influenced phosphate mineralization and inhibited metal sulfide genesis. Images PMID:16346230

  10. COMPLEX FLUORIDES OF PLUTONIUM AND AN ALKALI METAL

    DOEpatents

    Seaborg, G.T.

    1960-08-01

    A method is given for precipitating alkali metal plutonium fluorides. such as KPuF/sub 5/, KPu/sub 2/F/sub 9/, NaPuF/sub 5/, and RbPuF/sub 5/, from an aqueous plutonium(IV) solution by adding hydrogen fluoride and alkali-metal- fluoride.

  11. Process for the displacement of cyanide ions from metal-cyanide complexes

    DOEpatents

    Smith, Barbara F.; Robinson, Thomas W.

    1997-01-01

    The present invention relates to water-soluble polymers and the use of such water-soluble polymers in a process for the displacement of the cyanide ions from the metal ions within metal-cyanide complexes. The process waste streams can include metal-cyanide containing electroplating waste streams, mining leach waste streams, mineral processing waste streams, and related metal-cyanide containing waste streams. The metal ions of interest are metals that give very strong complexes with cyanide, mostly iron, nickel, and copper. The physical separation of the water-soluble polymer-metal complex from the cyanide ions can be accomplished through the use of ultrafiltration. Once the metal-cyanide complex is disrupted, the freed cyanide ions can be recovered for reuse or destroyed using available oxidative processes rendering the cyanide nonhazardous. The metal ions are released from the polymer, using dilute acid, metal ion oxidation state adjustment, or competing chelating agents, and collected and recovered or disposed of by appropriate waste management techniques. The water-soluble polymer can then be recycled. Preferred water-soluble polymers include polyethyleneimine and polyethyleneimine having a catechol or hydroxamate group.

  12. Modelling of trace metal uptake by roots taking into account complexation by exogenous organic ligands

    NASA Astrophysics Data System (ADS)

    Jean-Marc, Custos; Christian, Moyne; Sterckeman, Thibault

    2010-05-01

    The context of this study is phytoextraction of soil trace metals such as Cd, Pb or Zn. Trace metal transfer from soil to plant depends on physical and chemical processes such as minerals alteration, transport, adsorption/desorption, reactions in solution and biological processes including the action of plant roots and of associated micro-flora. Complexation of metal ions by organic ligands is considered to play a role on the availability of trace metals for roots in particular in the event that synthetic ligands (EDTA, NTA, etc.) are added to the soil to increase the solubility of the contaminants. As this role is not clearly understood, we wanted to simulate it in order to quantify the effect of organic ligands on root uptake of trace metals and produce a tool which could help in optimizing the conditions of phytoextraction.We studied the effect of an aminocarboxilate ligand on the absorption of the metal ion by roots, both in hydroponic solution and in soil solution, for which we had to formalize the buffer power for the metal. We assumed that the hydrated metal ion is the only form which can be absorbed by the plants. Transport and reaction processes were modelled for a system made up of the metal M, a ligand L and the metal complex ML. The Tinker-Nye-Barber model was adapted to describe the transport of solutes M, L and ML in the soil and absorption of M by the roots. This allowed to represent the interactions between transport, chelating reactions, absorption of the solutes at the root surface, root growth with time, in order to simulate metal uptake by a whole root system.Several assumptions were tested such as i) absorption of the metal by an infinite sink and according to a Michaelis-Menten kinetics, solutes transport by diffusion with and without ii) mass flow and iii) soil buffer power for the ligand L. In hydroponic solution (without soil buffer power), ligands decreased the trace metal flux towards roots, as they reduced the concentration of hydrated

  13. Design, synthesis, structural elucidation, pharmacological evaluation of metal complexes with pyrazoline derivatives.

    PubMed

    Muneera, M Sirajul; Joseph, J

    2016-10-01

    A bioactive pyrazoline derivatives have been synthesized by the base-catalyzed Claisen-Schmidt condensation of imidazole-2-carboxaldehyde with 1-acetyl-2-hydroxynaphthalene followed by cyclization with phenylhydrazine (L(1))/2,3-dimethylphenylhydrazine (L(2)) and 3-nitrophenylhydrazine (L(3)). The metal(II) complexes [Ni(II), Co(II), Cu(II) and Zn(II)] were formed by reacting the corresponding metal acetates with the ligands. All complexes were characterized by elemental analyses, electronic, IR, NMR, mass and ESR spectroscopic techniques. The synthesized metal complexes of pyrazoline compounds showed significant antibacterial activity against the organisms Escherichia coli, Staphylococcus aureus, Klebsiella pneumoniae, Proteus mirabilis and Salmonella typhii when compared with the standard antibiotic (Streptomycin). The ligands and their metal complexes were screened for antioxidant activity using DPPH radical scavenging and superoxide radical scavenging assay methods. All the complexes showed good free radical scavenging activity which is comparable to that of the standards. Among the metal complexes, the copper complex has showed higher activity. The results were indicated that 2-pyrazoline (structural core) and copper ion could be responsible for the potential candidate eliciting antioxidant activity. All compounds were evaluated for their in vitro antimycobacterial activity against Mycobacterium tuberculosis. The ligands and metal complexes were subjected to fluorescence properties and exhibited that the variable fluorescence emission behavior of complexes. It can be attributed to the combined effect of the substituents and naphthyl structural core present in the ligands.

  14. Microwave Assisted Synthesis, Characterisation and Fluorescence Studies of some Transition Metal Complexes with a Luminol Derivative.

    PubMed

    Aswathy, R; Mohanan, K

    2017-03-07

    A novel heterocyclic luminol derivative was synthesized by coupling diazotized 5-aminophthalhydrazide with 2-naphthol. This compound viz., Phthalhydrazide-5-azo-2-naphthol is versatile in forming stable metal complexes with cobalt(II), nickel(II), copper(II) and zinc(II) ions under microwave assisted solvent free conditions. The ligand and the metal complexes were characterized on the basis of elemental analyses, molar conductance, magnetic susceptibility measurements, UV-Visible, IR, (1)H NMR, and ESR spectral studies wherever possible and applicable. The fluorescence spectra of the ligand and its metal complexes were also recorded. The fluorescence life time measurements were conducted and it was observed that binding of the ligand to the metal ion decreases the average life time of the metal complexes.

  15. Multiheteromacrocycles that Complex Metal Ions. Sixth Progress Report, 1 May 1979-30 April 1980

    DOE R&D Accomplishments Database

    Cram, D. J.

    1980-01-15

    Objective is to design synthesize, and evaluate cyclic and polycyclic host organic compounds for their abilities to complex and lipophilize guest metal ions, their complexes, and their clusters. Host organic compounds consist of strategically placed solvating, coordinating, and ion-pairing sites tied together by covalent bonds through hydrocarbon units around cavities shaped to be occupied by guest metal ions or by metal ions plus their ligands. Specificity in complexation is sought by matching the following properties of host and guest: cavity and metal ion sizes; geometric arrangements of binding sites; number of binding sites; character of binding sites; and valences. During this period, hemispherands based on an aryloxy or cyclic urea unit, spherands based on aryloxyl units only, and their complexes with alkali metals and alkaline earths were investigated. An attempt to separate {sup 6}Li and {sup 7}Li by gel permeation chromatography of lithiospherium chloride failed. (DLC)

  16. Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

    DOEpatents

    Lilga, Michael A.; Hallen, Richard T.

    1991-01-01

    The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately .pi.-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancilliary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H.sub.2 from mixed gas streams such as the product gas from coal gasification processes.

  17. Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

    DOEpatents

    Lilga, Michael A.; Hallen, Richard T.

    1990-01-01

    The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately .pi.-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancilliary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H.sub.2 from mixed gas streams such as the produce gas from coal gasification processes.

  18. Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

    DOEpatents

    Lilga, M.A.; Hallen, R.T.

    1991-10-15

    The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately [pi]-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancillary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H[sub 2] from mixed gas streams such as the product gas from coal gasification processes. 3 figures.

  19. Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

    DOEpatents

    Lilga, M.A.; Hallen, R.T.

    1990-08-28

    The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately [pi]-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancillary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H[sub 2] from mixed gas streams such as the producer gas from coal gasification processes. 3 figs.

  20. New directions in the science and technology of advanced sheet explosive formulations and the key energetic materials used in the processing of sheet explosives: Emerging trends.

    PubMed

    Talawar, M B; Jangid, S K; Nath, T; Sinha, R K; Asthana, S N

    2015-12-30

    This review presents the work carried out by the international community in the area of sheet explosive formulations and its applications in various systems. The sheet explosive is also named as PBXs and is a composite material in which solid explosive particles like RDX, HMX or PETN are dispersed in a polymeric matrix, forms a flexible material that can be rolled/cut into sheet form which can be applied to any complex contour. The designed sheet explosive must possess characteristic properties such as flexible, cuttable, water proof, easily initiable, and safe handling. The sheet explosives are being used for protecting tanks (ERA), light combat vehicle and futuristic infantry carrier vehicle from different attacking war heads etc. Besides, sheet explosives find wide applications in demolition of bridges, ships, cutting and metal cladding. This review also covers the aspects such as risks and hazard analysis during the processing of sheet explosive formulations, effect of ageing on sheet explosives, detection and analysis of sheet explosive ingredients and the R&D efforts of Indian researchers in the development of sheet explosive formulations. To the best of our knowledge, there has been no review article published in the literature in the area of sheet explosives.

  1. Metal-isonitrile adducts for preparing radionuclide complexes for labelling and imaging agents

    DOEpatents

    Jones, Alun G.; Davison, Alan; Abrams, Michael J.

    1987-01-01

    A method for preparing a coordination complex of an isonitrile ligand and radionuclide such as Tc, Ru, Co, Pt, Fe, Os, Ir, W, Re, Cr, Mo, Mn, Ni, Rh, Pd, Nb and Ta is disclosed. The method comprises preparing a soluble metal adduct of said isonitrile ligand by admixing said ligand with a salt of a displaceable metal having a complete d-electron shell selected from the group consisting of Zn, Ga, Cd, In, Sn, Hg, Tl, Pb and Bi to form a soluble metal-isonitrile salt, and admixing said metal isonitrile salt with a salt comprising said radioactive metal in a suitable solvent to displace said displaceable metal with the radioactive metal thereby forming said coordination. The complex is useful as a diagnostic agent for labelling liposomes or vesicles, and selected living cells containing lipid membranes, such as blood clots, myocardial tissue, gall bladder tissue, etc.

  2. Structures and energetics of complexation of metal ions with ammonia, water, and benzene: A computational study.

    PubMed

    Sharma, Bhaskar; Neela, Y Indra; Narahari Sastry, G

    2016-04-30

    Quantum chemical calculations have been performed at CCSD(T)/def2-TZVP level to investigate the strength and nature of interactions of ammonia (NH3 ), water (H2 O), and benzene (C6 H6 ) with various metal ions and validated with the available experimental results. For all the considered metal ions, a preference for C6 H6 is observed for dicationic ions whereas the monocationic ions prefer to bind with NH3 . Density Functional Theory-Symmetry Adapted Perturbation Theory (DFT-SAPT) analysis has been employed at PBE0AC/def2-TZVP level on these complexes (closed shell), to understand the various energy terms contributing to binding energy (BE). The DFT-SAPT result shows that for the metal ion complexes with H2 O electrostatic component is the major contributor to the BE whereas, for C6 H6 complexes polarization component is dominant, except in the case of alkali metal ion complexes. However, in case of NH3 complexes, electrostatic component is dominant for s-block metal ions, whereas, for the d and p-block metal ion complexes both electrostatic and polarization components are important. The geometry (M(+) -N and M(+) -O distance for NH3 and H2 O complexes respectively, and cation-π distance for C6 H6 complexes) for the alkali and alkaline earth metal ion complexes increases down the group. Natural population analysis performed on NH3 , H2 O, and C6 H6 complexes shows that the charge transfer to metal ions is higher in case of C6 H6 complexes.

  3. Spectral, XRD, SEM and biological activities of transition metal complexes of polydentate ligands containing thiazole moiety

    NASA Astrophysics Data System (ADS)

    Neelakantan, M. A.; Marriappan, S. S.; Dharmaraja, J.; Jeyakumar, T.; Muthukumaran, K.

    2008-11-01

    Metal complexes of o-vanillidene-2-aminobenzothiazole have been prepared and characterized by elemental and spectral (vibrational, electronic, 1H NMR and EPR) data as well as magnetic susceptibility measurements and thermo gravimetric analysis (TG/DTA). The low molar conductance values reveal the non-electrolytic nature of these complexes. The elemental analysis suggests that the stoichiometry to be 1:2 (metal:ligand). Magnetic susceptibility data coupled with electronic spectra suggest that two ligands coordinate to each metal atom by phenolic oxygen and imino nitrogen to form high spin octahedral complex with Co(II), Mn(II) and Ni(II). The fifth and sixth position of metal ion is satisfied with water molecules. The thermal behaviour (TG/DTA) of the synthesised complexes shows that the complexes loss water molecules in the first step followed by decomposition of the ligand. Spin Hamiltonian parameters predict a distorted tetrahedral geometry for the copper complex. XRD and SEM analysis provide the crystalline nature and the morphology of the metal complexes. The in vitro biological activity of the metal chelates is tested against the Gram positive bacteria ( Bacillus amyloliquifacians) and gram negative bacteria ( Pseudomonas species), fungus ( Aspergillus niger) and yeast ( Sacchromyces cereviaceae). Most of the metal chelates exhibited higher biological activities.

  4. Electronic Spectra of TRIS(2,2'-BIPYRIDINE)-METAL Complex Ions in Gas Phase

    NASA Astrophysics Data System (ADS)

    Xu, Shuang; Smith, James E. T.; Weber, J. Mathias

    2016-06-01

    Tris(bpy)-metal complexes (bpy = 2,2'-bipyridine) and their derivatives are important systems in metal-organic chemistry. While tris(bpy)-ruthenium, Ru(bpy)32+, has been extensively studied, less attention has been paid to analogous complexes involving first row transition metals. Here we report the electronic spectra of a series of dicationic tris(bpy) chelates with different transition metals, measured by photodisscociation spectroscopy of cryogenically prepared ions. We focus our attention on the π-π* transitions in the UV region of the spectrum.

  5. Application of Δ- and Λ-Isomerism of Octahedral Metal Complexes for Inducing Chiral Nematic Phases

    PubMed Central

    Sato, Hisako; Yamagishi, Akihiko

    2009-01-01

    The Δ- and Λ-isomerism of octahedral metal complexes is employed as a source of chirality for inducing chiral nematic phases. By applying a wide range of chiral metal complexes as a dopant, it has been found that tris(β-diketonato)metal(III) complexes exhibit an extremely high value of helical twisting power. The mechanism of induction of the chiral nematic phase is postulated on the basis of a surface chirality model. The strategy for designing an efficient dopant is described, together with the results using a number of examples of Co(III), Cr(III) and Ru(III) complexes with C2 symmetry. The development of photo-responsive dopants to achieve the photo-induced structural change of liquid crystal by use of photo-isomerization of chiral metal complexes is also described. PMID:20057959

  6. Effect of entropy-packing fraction relation on the formation of complex metallic materials

    NASA Astrophysics Data System (ADS)

    Tourki Samaei, Arash; Mohammadi, Ehsan

    2015-09-01

    By combining a number of elements to form complex metallic materials without a base element, it was recently shown that one can obtain rather complex structures, including random solute solutions, multi-phased mixtures and amorphous structures with/without nano-precipitations. Compared to conventional metallic materials, these complex ones could show excellent mechanical and physical properties across a wide range of temperatures, therefore being a promising advanced material for high-temperature applications; however, designing these complex materials, at present, still lacks a unified physical approach but relies on the choice of a few metallurgical parameters, such as atomic size mismatch, heat of mixing and valence electron concentration. Here, we identify a physical mechanism through the optimization of the excess configurational entropy of mixing in the control of phase formation in these metallic materials. The theoretical framework herein established is expected to provide a new paradigm in pursuit of complex metallic materials with superior properties.

  7. A survey of the mechanisms of action of anticancer transition metal complexes.

    PubMed

    Marloye, Mickaël; Berger, Gilles; Gelbcke, Michel; Dufrasne, François

    2016-12-01

    Metal complexes have been the subject of numerous investigations in oncology but, despite the plethora of newly synthesized compounds, their precise mechanisms of action remain generally unknown or, for the best, incompletely determined. The continuous development of efficient and sensitive techniques in analytical chemistry and molecular biology gives scientists new tools to gather information on how metal complexes can be effective toward cancer. This review focuses on recent findings about the anticancer mechanism of action of metal complexes and how the ligands can be used to tune their pharmacological and physicochemical properties.

  8. Asymmetric catalysis mediated by the ligand sphere of octahedral chiral-at-metal complexes.

    PubMed

    Gong, Lei; Chen, Liang-An; Meggers, Eric

    2014-10-06

    Due to the relationship between structure and function in chemistry, access to novel chemical structures ultimately drives the discovery of novel chemical function. In this light, the formidable utility of the octahedral geometry of six-coordinate metal complexes is founded in its stereochemical complexity combined with the ability to access chemical space that might be unavailable for purely organic compounds. In this Minireview we wish to draw attention to inert octahedral chiral-at-metal complexes as an emerging class of metal-templated asymmetric "organocatalysts" which exploit the globular, rigid nature and stereochemical options of octahedral compounds and promise to provide new opportunities in the field of catalysis.

  9. New trends in the optical and electronic applications of polymers containing transition-metal complexes.

    PubMed

    Liu, Shu-Juan; Chen, Yang; Xu, Wen-Juan; Zhao, Qiang; Huang, Wei

    2012-04-13

    Polymers containing transition-metal complexes exhibit excellent optical and electronic properties, which are different from those of polymers with a pure organic skeleton and combine the advantages of both polymers and metal complexes. Hence, research about this class of polymers has attracted more and more interest in recent years. Up to now, a number of novel polymers containing transition-metal complexes have been exploited, and significant advances in their optical and electronic applications have been achieved. In this article, we summarize some new research trends in the applications of this important class of optoelectronic polymers, such as chemo/biosensors, electronic memory devices and photovoltaic devices.

  10. Metal complexes of curcumin--synthetic strategies, structures and medicinal applications.

    PubMed

    Wanninger, Simon; Lorenz, Volker; Subhan, Abdus; Edelmann, Frank T

    2015-08-07

    This Tutorial Review presents an overview on the synthesis, characterization and applications of metal complexes containing curcumin (=1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione) and its derivatives as ligands. Innovative synthetic strategies leading to soluble and crystallizable metal curcumin complexes are outlined in detail. Special emphasis is placed on the highly promising and exciting medicinal applications of metal curcumin complexes, with the three most important areas being anticancer activity and selective cytotoxicity, anti-Alzheimer's disease activity, and antioxidative/neuroprotective effects. Overall, this Tutorial Review provides the first general overview of this emerging and rapidly expanding field of interdisciplinary research.

  11. Bonding in diborane-metal complexes: a quantum-chemical and experimental study of complexes featuring early and late transition metals.

    PubMed

    Wagner, Arne; Kaifer, Elisabeth; Himmel, Hans-Jörg

    2013-06-03

    The coordination chemistry of the doubly base-stabilised diborane(4), [HB(hpp)]2 (hpp = 1,3,4,6,7,8-hexahydro-2H-pyrimido-[1,2-a]pyrimidinate), was extended by the synthesis of new late transition-metal complexes containing Cu(I) and Rh(I) fragments. A detailed experimental study was conducted and quantum-chemical calculations on the metal-ligand bonding interactions for [HB(hpp)]2 complexes of Group 6, 9, 11 and 12 metals revealed the dominant B-H-M interactions in the case of early transition-metal fragments, whereas the B-B-M bonding prevails in the case of the late d-block compounds. These findings support the experimental results as reflected by the IR and NMR spectroscopic parameters of the investigated compounds. DFT calculations on [MeB(hpp)]2 and model reactions between [B2H4⋅2NMe3] and [Rh(μ-Cl)(C2H4)2] showed that the bicyclic guanidinate allows in principle for an oxidative addition of the B-B bond. However, the formation of σ-complexes is thermodynamically favoured. The results point to the selective B-H or B-B bond-activation of diborane compounds by complexation, depending on the chosen transition-metal fragment.

  12. Transition metal complexes supported on metal-organic frameworks for heterogeneous catalysts

    DOEpatents

    Farha, Omar K.; Hupp, Joseph T.; Delferro, Massimiliano; Klet, Rachel C.

    2017-02-07

    A robust mesoporous metal-organic framework comprising a hafnium-based metal-organic framework and a single-site zirconium-benzyl species is provided. The hafnium, zirconium-benzyl metal-organic framework is useful as a catalyst for the polymerization of an alkene.

  13. Spectral and structural characterization of amidate-bridged platinum-thallium complexes with strong metal-metal bonds.

    PubMed

    Chen, Wanzhi; Liu, Fenghui; Matsumoto, Kazuko; Autschbach, Jochen; Le Guennic, Boris; Ziegler, Tom; Maliarik, Mikhail; Glaser, Julius

    2006-05-29

    The reactions of [Pt(NH3)2(NHCOtBu)2] and TlX3 (X = NO3-, Cl-, CF3CO2-) yielded dinuclear [{Pt(ONO2)(NH3)2(NHCOtBu)}Tl(ONO2)2(MeOH)] (2) and trinuclear complexes [{PtX(RNH2)2(NHCOtBu)2}2Tl]+ [X = NO3- (3), Cl- (5), CF3CO2- (6)], which were spectroscopically and structurally characterized. Strong Pt-Tl interaction in the complexes in solutions was indicated by both 195Pt and 205Tl NMR spectra, which exhibit very large one-bond spin-spin coupling constants between the heteronuclei (1J(PtTl)), 146.8 and 88.84 kHz for 2 and 3, respectively. Both the X-ray photoelectron spectra and the 195Pt chemical shifts reveal that the complexes have Pt centers whose oxidation states are close to that of Pt(III). Characterization of these complexes by X-ray diffraction analysis confirms that the Pt and Tl atoms are held together by very short Pt-Tl bonds and are supported by the bridging amidate ligands. The Pt-Tl bonds are shorter than 2.6 Angstrom, indicating a strong metal-metal attraction between these two metals. Compound 2 was found to activate the C-H bond of acetone to yield a platinum(IV) acetonate complex. This reactivity corresponds to the property of Pt(III) complexes. Density functional theory calculations were able to reproduce the large magnitude of the metal-metal spin-spin coupling constants. The couplings are sensitive to the computational model because of a delicate balance of metal 6s contributions in the frontier orbitals. The computational analysis reveals the role of the axial ligands in the magnitude of the coupling constants.

  14. Self-Assembly of Discrete Metal Complexes in Aqueous Solution via Block Copolypeptide Amphiphiles

    PubMed Central

    Kuroiwa, Keita; Masaki, Yoshitaka; Koga, Yuko; Deming, Timothy J.

    2013-01-01

    The integration of discrete metal complexes has been attracting significant interest due to the potential of these materials for soft metal-metal interactions and supramolecular assembly. Additionally, block copolypeptide amphiphiles have been investigated concerning their capacity for self-assembly into structures such as nanoparticles, nanosheets and nanofibers. In this study, we combined these two concepts by investigating the self-assembly of discrete metal complexes in aqueous solution using block copolypeptides. Normally, discrete metal complexes such as [Au(CN)2]−, when molecularly dispersed in water, cannot interact with one another. Our results demonstrated, however, that the addition of block copolypeptide amphiphiles such as K183L19 to [Au(CN)2]− solutions induced one-dimensional integration of the discrete metal complex, resulting in photoluminescence originating from multinuclear complexes with metal-metal interactions. Transmission electron microscopy (TEM) showed a fibrous nanostructure with lengths and widths of approximately 100 and 20 nm, respectively, which grew to form advanced nanoarchitectures, including those resembling the weave patterns of Waraji (traditional Japanese straw sandals). This concept of combining block copolypeptide amphiphiles with discrete coordination compounds allows the design of flexible and functional supramolecular coordination systems in water. PMID:23337202

  15. Characterization of metal-peptide complexes in feed supplements of essential trace elements.

    PubMed

    Yiannikouris, Alexandros; Connolly, Cathal; Power, Ronan; Lobinski, Ryszard

    2009-01-01

    Metal chelates with biomolecules are increasingly used in animal supplementation to increase the bioavailability of essential trace elements. However, the transfer of the chelates is not well understood and speciation studies may bring a comprehensive insight to further investigate the biological uptake mechanism(s) implicated. An analytical method was developed for the characterization of the water-soluble metal complexes in animal feed supplements obtained by reaction of a metal salt with a non-GMO soybean enzymatic digest. The method was based on fractionation of the extract by size-exclusion chromatography followed by the analysis of the metal-containing fraction by reversed-phase nanoHPLC with parallel ICP MS and electrospray MS/MS detection. The metal complexes were identified in the mass spectra owing to the Cu characteristic isotopic pattern; the complexation was corroborated by the presence of a peak corresponding to the non-metallated peptide. The study demonstrated the feasibility of SEC-ICP MS to produce characteristic metal (Cu, Zn, Mn, Fe) distribution patterns, which can be of interest to test batch-to-batch reproducibility and to determine the origin of the supplement. The use of the method could be extended to animal feeds prepared using the metal-chelated complexes. Electrospray MS/MS allowed the identification of a number of Cu complexes with peptides. Four different structure conformations were modeled by means of molecular mechanics investigations to assess the chelation stability.

  16. First row transition metal complexes of (E)-2-(2-(2-hydroxybenzylidene) hydrazinyl)-2-oxo-N-phenylacetamide complexes

    NASA Astrophysics Data System (ADS)

    Yousef, T. A.; Abu El-Reash, G. M.; Rakha, T. H.; El-Ayaan, Usama

    2011-12-01

    Manganese(II), iron(II), cobalt(II), nickel(II), copper(II), and chromium(III) complexes of (E)-2-(2-(2-hydroxybenzylidene)hydrazinyl)-2-oxo-N-phenylacetamide were synthesized and characterized by elemental and thermal (TG and DTA) analyses, IR, UV-vis and 1H NMR spectra as well as magnetic moment. Mononuclear complexes are obtained with 1:1 molar ratio except [Mn(HOS) 2(H 2O) 2] and [Co(OS) 2](H 2O) 2 complexes which are obtained with 1:2 molar ratios. The IR spectra of ligand and metal complexes reveal various modes of chelation. The ligand behaves as a monobasic bidentate one and coordination occurs via the enolic oxygen atom and azomethine nitrogen atom. The ligand behaves also as a monobasic tridentate one and coordination occurs through the carbonyl oxygen atom, azomethine nitrogen atom and the hydroxyl oxygen. Moreover, the ligand behaves as a dibasic tridentate and coordination occurs via the enolic oxygen, azomethine nitrogen and the hydroxyl oxygen atoms. The electronic spectra and magnetic moment measurements reveal that all complexes possess octahedral geometry except the copper complexes possesses a square planar geometry. From the modeling studies, the bond length, bond angle, HOMO, LUMO and dipole moment had been calculated to confirm the geometry of the ligands and their investigated complexes. The thermal studies showed the type of water molecules involved in metal complexes as well as the thermal decomposition of some metal complexes. The protonation constant of the ligand and the stability constant of metal complexes were determined pH-metrically in 50% (v/v) dioxane-water mixture at 298 K and found to be consistent with Irving-Williams order. Moreover, the minimal inhibitory concentration (MIC) of these compounds against Staphylococcus aureus, Escherechia coli and Candida albicans were determined.

  17. Coordination Chemistry of Disilylated Stannylenes with Group 10 d10 Transition Metals: Silastannene vs Stannylene Complexation

    PubMed Central

    2013-01-01

    The coordination behavior of disilylated stannylenes toward zerovalent group 10 transition metal complexes was studied. This was accomplished by reactions of PEt3 adducts of disilylated stannylenes with zerovalent group 10 transition metal complexes. The thus obtained products differed between the first row example nickel and its heavier congeners. While with nickel stannylene complex formation was observed, coordination of the stannylenes to palladium and platinum compounds led to unusual silastannene complexes of these metals. A computational model study indicated that in each case metal stannylene complexes were formed first and that the disilylstannylene/silastannene rearrangement occurs only after complexation to the group 10 metal. The isomerization is a two-step process with relatively small barriers, suggesting a thermodynamic control of product formation. In addition, the results of the computational investigation revealed a subtle balance of steric and electronic effects, which determines the relative stability of the metalastannylene complex relative to its silastannene isomer. In the case of cyclic disilylstannylenes, the Pd(0) and Pt(0) silastannene complexes are found to be more stable, while with acyclic disilylstannylenes the Ni(0) stannylene complex is formed preferentially. PMID:23627362

  18. Theoretical study of the rhenium-alkane interaction in transition metal-alkane sigma-complexes.

    PubMed

    Cobar, Erika A; Khaliullin, Rustam Z; Bergman, Robert G; Head-Gordon, Martin

    2007-04-24

    Metal-alkane binding energies have been calculated for [CpRe(CO)2](alkane) and [(CO)2M(C5H4)C[triple bond]C(C5H4)M(CO)2](alkane), where M = Re or Mn. Calculated binding energies were found to increase with the number of metal-alkane interaction sites. In all cases examined, the manganese-alkane binding energies were predicted to be significantly lower than those for the analogous rhenium-alkane complexes. The metal (Mn or Re)-alkane interaction was predicted to be primarily one of charge transfer, both from the alkane to the metal complex (70-80% of total charge transfer) and from the metal complex to the alkane (20-30% of the total charge transfer).

  19. Synthesis, Characterization, Antibacterial and Anti-Inflammatory Activities of Enoxacin Metal Complexes

    PubMed Central

    Arayne, Saeed; Sultana, Najma; Haroon, Urooj; Mesaik, M. Ahmed

    2009-01-01

    The present work comprises the synthesis of enoxacin (Heno) complexes with various transition metals. Two types of complexes [M(eno)2(H2O)2]3H2O(M = CuII, NiII or MnII) and [M(eno)(H2O)2]Cl · 4H2O (M = FeIII) were obtained. The complexes were characterized by different physicochemical, spectroscopic, and elemental analysis. Results suggest that enoxacin interacts with the metals as a monoanionic bidentate ligand. These complexes were also tested for their antibacterial activity against eleven (11) different microorganisms, and the results were compared with the parent drug. Moreover all the metal complexes were also tested for their ability to scavenge reactive oxygen species where by MnII and CuII complexes exhibited potential to mediate anti-inflammatory response. PMID:19657456

  20. Transition metal complexes of neocryptolepine analogues. Part I: synthesis, spectroscopic characterization, and invitro anticancer activity of copper(II) complexes.

    PubMed

    Emam, Sanaa Moustafa; El Sayed, Ibrahim El Tantawy; Nassar, Nagla

    2015-03-05

    New generation of copper(II) complexes with aminoalkylaminoneocryptolepine as bidentate ligands has been synthesized and it is characterized by elemental analyses, magnetic moment, spectra (IR, UV-Vis, (1)H NMR and ESR) and thermal studies. The IR data suggest the coordination modes for ligands which behave as a bidentate with copper(II) ion. Based on the elemental analysis, magnetic studies, electronic and ESR data, binuclear square planar geometry was proposed for complexes 7a, 7b, square pyramidal for 9a, 9b and octahedral for 8a, 8b, 10a, 10b. The molar conductance in DMF solution indicates that all complexes are electrolyte except 7a and 7b. The ESR spectra of solid copper(II) complexes in powder form showed an axial symmetry with (2)B1g as a ground state and hyperfine structure. The thermal stability and degradation of the ligands and their metal complexes were studied employing DTA and TG methods. The metal-free ligands and their copper(II) complexes were tested for their in vitro anticancer activity against human colon carcinoma (HT-29). The results showed that the synthesized copper(II) complexes exhibited higher anticancer activity than their free ligands. Of all the studied copper(II) complexes, the bromo-substituted complex 9b exhibited high anticancer activity at low micromolar inhibitory concentrations (IC50=0.58μM), compared to the other complexes and the free ligands.

  1. Transition metal complexes of neocryptolepine analogues. Part I: Synthesis, spectroscopic characterization, and invitro anticancer activity of copper(II) complexes

    NASA Astrophysics Data System (ADS)

    Emam, Sanaa Moustafa; El Sayed, Ibrahim El Tantawy; Nassar, Nagla

    2015-03-01

    New generation of copper(II) complexes with aminoalkylaminoneocryptolepine as bidentate ligands has been synthesized and it is characterized by elemental analyses, magnetic moment, spectra (IR, UV-Vis, 1H NMR and ESR) and thermal studies. The IR data suggest the coordination modes for ligands which behave as a bidentate with copper(II) ion. Based on the elemental analysis, magnetic studies, electronic and ESR data, binuclear square planar geometry was proposed for complexes 7a, 7b, square pyramidal for 9a, 9b and octahedral for 8a, 8b, 10a, 10b. The molar conductance in DMF solution indicates that all complexes are electrolyte except 7a and 7b. The ESR spectra of solid copper(II) complexes in powder form showed an axial symmetry with 2B1g as a ground state and hyperfine structure. The thermal stability and degradation of the ligands and their metal complexes were studied employing DTA and TG methods. The metal-free ligands and their copper(II) complexes were tested for their in vitro anticancer activity against human colon carcinoma (HT-29). The results showed that the synthesized copper(II) complexes exhibited higher anticancer activity than their free ligands. Of all the studied copper(II) complexes, the bromo-substituted complex 9b exhibited high anticancer activity at low micromolar inhibitory concentrations (IC50 = 0.58 μM), compared to the other complexes and the free ligands.

  2. Structure Characterization and Properties of Metal-Surfactant Complexes Dispersed in Organic Solvents.

    PubMed

    de la Iglesia, Pablo; Jaeger, Vance W; Xi, Yuyin; Pfaendtner, Jim; Pozzo, Lilo D

    2015-08-25

    This work describes the synthesis and characterization of metal-surfactant complexes. Dioctyl sulfosuccinate and dodecylbenzenesulfonate are associated with multivalent aluminum, iron, and vanadium ions using an ion exchange reaction. The metal complexes are dispersible in various organic solvents. In solvents with low polarity, the complexes form "inverse" macromolecular structures with multiple metal ions. In contrast, in alcohols, the complex size is reduced, showing a more disperse conformation. The metal and surfactant ions are still strongly bonded to each other in all the solvents probed. Small-angle X-ray and neutron scattering (SAXS and SANS) are used to characterize the structures. Simultaneous fitting of neutron and X-ray scattering spectra is performed in order to obtain an accurate description of the system. Scattering results are also validated by performing molecular dynamics (MD) simulations. The conductive and electrochemical properties of the complexes in solution are also evaluated. The dispersion of metal-organic complexes significantly increases electric conductivity, and some metal ions in the core of the complexes are shown to be electrochemically active in apolar solvents.

  3. IRMPD Spectroscopy of Metalated Flavins: Structure and Bonding of Lumiflavin Complexes with Alkali and Coinage Metal Ions.

    PubMed

    Nieto, Pablo; Günther, Alan; Berden, Giel; Oomens, Jos; Dopfer, Otto

    2016-10-01

    Flavins are a fundamental class of biomolecules, whose photochemical properties strongly depend on their environment and their redox and metalation state. Infrared multiphoton dissociation (IRMPD) spectra of mass selected isolated metal-lumiflavin ionic complexes (M+LF) are analyzed in the fingerprint range (800-1830 cm-1) to determine the bonding of lumiflavin with alkali (M=Li, Na, K, Cs) and coinage (M=Cu, Ag) metal ions. The complexes are generated in an electrospray ionization source coupled to an ion cyclotron resonance mass spectrometer and the IR free electron laser FELIX. Vibrational and isomer assignments of the IRMPD spectra are accomplished by comparison to quantum chemical calculations at the B3LYP/cc-pVDZ level, yielding structure, binding energy, bonding mechanism, and spectral properties of the complexes. The most stable binding sites identified in the experiments involve metal bonding to the oxygen atoms of the two available CO groups of LF. Hence, CO stretching frequencies are a sensitive indicator of both the metal binding site and the metal bond strength. More than one isomer is observed for M=Li, Na, and K, and the preferred CO binding site changes with the size of the alkali ion. For Cs+LF only one isomer is identified although the energies of the two most stable structures differ by less than 7 kJ/mol. While the M+-LF bonds for alkali ions are mainly based on electrostatic forces, substantial covalent contributions lead to stronger bonds for the coinage metal ions. Comparison between lumiflavin and lumichrome reveals substantial differences in the metal binding motifs and interactions due to the different flavin structures.

  4. Interaction of metal ions with biomolecular ligands: how accurate are calculated free energies associated with metal ion complexation?

    PubMed

    Gutten, Ondrej; Beššeová, Ivana; Rulíšek, Lubomír

    2011-10-20

    To address fundamental questions in bioinorganic chemistry, such as metal ion selectivity, accurate computational protocols for both the gas-phase association of metal-ligand complexes and solvation/desolvation energies of the species involved are needed. In this work, we attempt to critically evaluate the performance of the ab initio and DFT electronic structure methods available and recent solvation models in calculations of the energetics associated with metal ion complexation. On the example of five model complexes ([M(II)(CH(3)S)(H(2)O)](+), [M(II)(H(2)O)(2)(H(2)S)(NH(3))](2+), [M(II)(CH(3)S)(NH(3))(H(2)O)(CH(3)COO)], [M(II)(H(2)O)(3)(SH)(CH(3)COO)(Im)], [M(II)(H(2)S)(H(2)O)(CH(3)COO)(PhOH)(Im)](+) in typical coordination geometries) and four metal ions (Fe(2+), Cu(2+), Zn(2+), and Cd(2+); representing open- and closed-shell and the first- and second-row transition metal elements), we provide reference values for the gas-phase complexation energies, as presumably obtained using the CCSD(T)/aug-cc-pVTZ method, and compare them with cheaper methods, such as DFT and RI-MP2, that can be used for large-scale calculations. We also discuss two possible definitions of interaction energies underlying the theoretically predicted metal-ion selectivity and the effect of geometry optimization on these values. Finally, popular solvation models, such as COSMO-RS and SMD, are used to demonstrate whether quantum chemical calculations can provide the overall free enthalpy (ΔG) changes in the range of the expected experimental values for the model complexes or match the experimental stability constants in the case of three complexes for which the experimental data exist. The data presented highlight several intricacies in the theoretical predictions of the experimental stability constants: the covalent character of some metal-ligand bonds (e.g., Cu(II)-thiolate) causing larger errors in the gas-phase complexation energies, inaccuracies in the treatment of solvation of the

  5. A biphasic scaffold design combined with cell sheet technology for simultaneous regeneration of alveolar bone/periodontal ligament complex.

    PubMed

    Vaquette, Cédryck; Fan, Wei; Xiao, Yin; Hamlet, Stephen; Hutmacher, Dietmar W; Ivanovski, Saso

    2012-08-01

    This study describes the design of a biphasic scaffold composed of a Fused Deposition Modeling scaffold (bone compartment) and an electrospun membrane (periodontal compartment) for periodontal regeneration. In order to achieve simultaneous alveolar bone and periodontal ligament regeneration a cell-based strategy was carried out by combining osteoblast culture in the bone compartment and placement of multiple periodontal ligament (PDL) cell sheets on the electrospun membrane. In vitro data showed that the osteoblasts formed mineralized matrix in the bone compartment after 21 days in culture and that the PDL cell sheet harvesting did not induce significant cell death. The cell-seeded biphasic scaffolds were placed onto a dentin block and implanted for 8 weeks in an athymic rat subcutaneous model. The scaffolds were analyzed by μCT, immunohistochemistry and histology. In the bone compartment, a more intense ALP staining was obtained following seeding with osteoblasts, confirming the μCT results which showed higher mineralization density for these scaffolds. A thin mineralized cementum-like tissue was deposited on the dentin surface for the scaffolds incorporating the multiple PDL cell sheets, as observed by H&E and Azan staining. These scaffolds also demonstrated better attachment onto the dentin surface compared to no attachment when no cell sheets were used. In addition, immunohistochemistry revealed the presence of CEMP1 protein at the interface with the dentine. These results demonstrated that the combination of multiple PDL cell sheets and a biphasic scaffold allows the simultaneous delivery of the cells necessary for in vivo regeneration of alveolar bone, periodontal ligament and cementum.

  6. Alkane oxidation with porphyrins and metal complexes thereof having haloalkyl side chains

    DOEpatents

    Wijesekera, T.; Lyons, J.E.; Ellis, P.E. Jr.; Bhinde, M.V.

    1998-06-23

    Transition metal complexes of meso-haloalkylporphyrins are disclosed, wherein the haloalkyl groups contain 2 to 8 carbon atoms have been found to be highly effective catalysts for oxidation of alkanes and for the decomposition of hydroperoxides. 7 figs.

  7. Alkane oxidation with porphyrins and metal complexes thereof having haloalkyl side chains

    DOEpatents

    Wijesekera, Tilak; Lyons, James E.; Ellis, Jr., Paul E.; Bhinde, Manoj V.

    1998-01-01

    Transition metal complexes of meso-haloalkylporphyrins, wherein the haloalkyl groups contain 2 to 8 carbon atoms have been found to be highly effective catalysts for oxidation of alkanes and for the decomposition of hydroperoxides.

  8. The diastereoselective synthesis of octahedral cationic iridium hydride complexes with a stereogenic metal centre.

    PubMed

    Humbert, Nicolas; Mazet, Clément

    2016-08-23

    We report herein the highly diastereoselective synthesis of octahedral cationic Ir(iii) hydride complexes with a stereogenic metal centre following various strategies. The configurational stability of these compounds has also been investigated.

  9. Influence of phytic acid and its metal complexes on the activity of pectin degrading polygalacturonase.

    PubMed

    Asghar, Uzma; Rehman, Haneef Ur; Qader, Shah Ali Ul; Maqsood, Zahida Tasneem

    2013-06-05

    Polygalacturonase is one of the important requirements of different microorganism to cause pathogenicity and spoilage of fruits and vegetables that involved in degradation of pectin during plant tissue infections. In current study, 20 mM phytic acid inhibited 70% activity of polygalacturonase. The effect of different concentration of metal ions such as Cu(+2), Al(+3) and V(+4) were studied separately and it was found that the 20 mM of these metal ions inhibited 37.2%, 79%, and 53% activity of polygalacturonase, respectively. Finally, the complexes of phytic acid and these metals ions were prepared and 1:1 ratio of phytic acid and metal ions complexes showed maximum inhibitory activity of enzyme as compared to complexes having 1:2 and 1:3 ratio except phytate-copper complexes which showed no inhibitory effect on the activity of polygalacturonase.

  10. Reactivity of halide and pseudohalide ligands in transition-metal complexes

    SciTech Connect

    Kukushkin, Yu.N.; Kukushkin, V.Yu.

    1985-10-01

    The experimental material on the reactions of coordinated halide ligands, as well as cyanide, azido, thiocyanato, and cyanato ligands, in transition-metal complexes has been generalized in this review.

  11. Manipulation of a Schlenk Line: Preparation of Tetrahydrofuran Complexes of Transition-Metal Chlorides

    ERIC Educational Resources Information Center

    Davis, Craig M.; Curran, Kelly A.

    2007-01-01

    Before taking an inorganic laboratory course few students have experience handling air-sensitive materials using Schlenk techniques. This exercise introduces them to techniques they will employ in later syntheses. The procedure involves the formation of anhydrous tetrahydrofuran complexes of transition-metal chlorides from metal-chloride hydrates;…

  12. Synthesis, characterization, and biocide properties of semicarbazide-formaldehyde resin and its polymer metal complexes.

    PubMed

    Nishat, Nahid; Ahamad, Tansir; Alshehri, Saad M; Parveen, Shadma

    2010-04-01

    Semicarbazide-formaldehyde resin (SFRs) was prepared by the condensation of semicarbazide with formaldehyde in an acidic medium and its polymer metal complexes were prepared with transition metal ions. All the synthesized polymers were characterized by elemental analysis, FTIR, (1)H NMR, (13)C NMR, electronic spectroscopy, magnetic moment measurement and thermogravimetric analyses. The percentage of metal in all the polymer metal complexes was found to be consistent with 2:1 (resin: metal) stoichiometry. The magnetic susceptibility measurement and electronic spectra of all the polymer metal complexes confirmed the geometry of the complexes. All the synthesized polymeric compounds have been screened in vitro against Bacillus subtilis, Staphylococcus aureus (Gram-positive) and Escherichia coli, Salmonella typhi (Gram-negative) using shaking flask method. The entire polymer metal complexes showed excellent anti-bacterial activity and low toxicity when compared with their parental polymeric resin. The anti-bacterial activity and toxicity of the entire synthesized compound is significant and they can be used as antimicrobial as well as anticancer agents for mammals in future.

  13. Pyridinediimine Iron Complexes with Pendant Redox-Inactive Metals Located in the Secondary Coordination Sphere.

    PubMed

    Delgado, Mayra; Ziegler, Joshua M; Seda, Takele; Zakharov, Lev N; Gilbertson, John D

    2016-01-19

    A series of pyridinediimine (PDI) iron complexes that contain a pendant 15-crown-5 located in the secondary coordination sphere were synthesized and characterized. The complex Fe((15c5)PDI)(CO)2 (2) was shown in both the solid state and solution to encapsulate redox-inactive metal ions. Modest shifts in the reduction potential of the metal-ligand scaffold were observed upon encapsulation of either Na(+) or Li(+).

  14. Electropositive bivalent metallic ion unsaturated polyester complexed polymer concrete

    DOEpatents

    Sugama, T.; Kukacka, L.E.; Horn, W.H.

    1981-11-04

    Quick setting polymer concrete compositions which are mixtures of unsaturated polyesters and crosslinking monomers together with appropriate initiators and promoters in association with aggregate which may be wet and a source of bivalent metallic ions which will set to polymer concrete with excellent structural properties.

  15. Electropositive bivalent metallic ion unsaturated polyester complexed polymer concrete

    DOEpatents

    Sugama, T.; Kukacka, L.E.; Horn, W.H.

    1983-05-13

    Quick setting polymer concrete compositions are described which are mixtures of unsaturated polyesters and crosslinking monomers together with appropriate initiators and promoters in association with aggregate which may be wet and a source of bivalent metallic ions which will set to polymer concrete with excellent structural properties.

  16. Electropositive bivalent metallic ion unsaturated polyester complexed polymer concrete

    DOEpatents

    Sugama, Toshifumi; Kukacka, Lawrence E.; Horn, William H.

    1985-01-01

    Quick setting polymer concrete compositions with excellent structural properties are disclosed; these polymer concrete compositions are mixtures of unsaturated polyesters and crosslinking monomers together with appropriate initiators and promoters in association with aggregate, which may be wet, and with a source of bivalent metallic ions.

  17. Dissolution of Fe(III)(hydr) oxides by metal-EDTA complexes

    SciTech Connect

    Nowack, B.; Sigg, L. |

    1997-03-01

    The dissolution of Fe(III)(hydr)oxides (goethite and hydrous ferric oxide) by metal-EDTA complexes occurs by ligand-promoted dissolution. The process is initiated by the adsorption of metal-EDTA complexes to the surface and is followed by the dissociation of the complex at the surface and the release of Fe(III)EDTA into solution. The dissolution rate is decreased to a great extent if EDTA is complexed by metals in comparison to the uncomplexed EDTA. The rate decreases in the order EDTA > CaEDTA > PbEDTA > ZnEDTA > CuEDTA > Co(II)EDTA > NiEDTA. Two different rate-limiting steps determine the dissolution process: (1) detachment of Fe(III) from the oxide-structure and (2) dissociation of the metal-EDTA complexes. In the case of goethite, step 1 is slower than step 2 and the dissolution rates by various metals are similar. In the case of hydrous ferric oxide, step 2 is rate-limiting and the effect of the complexed metal is very pronounced. 35 refs., 11 figs., 4 tabs.

  18. Brønsted-Lowry Acid Strength of Metal Hydride and Dihydrogen Complexes.

    PubMed

    Morris, Robert H

    2016-08-10

    Transition metal hydride complexes are usually amphoteric, not only acting as hydride donors, but also as Brønsted-Lowry acids. A simple additive ligand acidity constant equation (LAC for short) allows the estimation of the acid dissociation constant Ka(LAC) of diamagnetic transition metal hydride and dihydrogen complexes. It is remarkably successful in systematizing diverse reports of over 450 reactions of acids with metal complexes and bases with metal hydrides and dihydrogen complexes, including catalytic cycles where these reactions are proposed or observed. There are links between pKa(LAC) and pKa(THF), pKa(DCM), pKa(MeCN) for neutral and cationic acids. For the groups from chromium to nickel, tables are provided that order the acidity of metal hydride and dihydrogen complexes from most acidic (pKa(LAC) -18) to least acidic (pKa(LAC) 50). Figures are constructed showing metal acids above the solvent pKa scales and organic acids below to summarize a large amount of information. Acid-base features are analyzed for catalysts from chromium to gold for ionic hydrogenations, bifunctional catalysts for hydrogen oxidation and evolution electrocatalysis, H/D exchange, olefin hydrogenation and isomerization, hydrogenation of ketones, aldehydes, imines, and carbon dioxide, hydrogenases and their model complexes, and palladium catalysts with hydride intermediates.

  19. Laminated sheet composites reinforced with modular filament sheet

    NASA Technical Reports Server (NTRS)

    Reece, O. Y.

    1968-01-01

    Aluminum and magnesium composite sheet laminates reinforced with low density, high strength modular filament sheets are produced by diffusion bonding and explosive bonding. Both processes are accomplished in normal atmosphere and require no special tooling or cleaning other than wire brushing the metal surfaces just prior to laminating.

  20. Stability constants of some metal complexes of triethylenetetraminehexa-acetic acid and complexometric titration of rare earths and other metals.

    PubMed

    Soucek, D A; Cheng, K L; Droll, H A

    1968-08-01

    The stability constants of some non-protonated 1:1 metal complexes of triethylenetetraminehexa-acetic acid are reported; log K values are Cd 19.8, Co(II) 20.4, Ni 19.9, Pb 19.5, Sm(III) 24.3, Zn 20.1.

  1. Recovery of nickel and cobalt from organic acid complexes: adsorption mechanisms of metal-organic complexes onto aminophosphonate chelating resin.

    PubMed

    Deepatana, A; Valix, M

    2006-09-21

    This study examined the recovery of nickel and cobalt from organic acid complexes using a chelating aminophosphonate Purolite S950 resin. These metal complexes are generated by bioleaching nickel laterite ores, a commercial nickel and cobalt mineral oxide, with heterotrophic organism and their metabolites or organic acid products. Equilibrium adsorption tests were conducted as a function of Ni and Co concentrations (15-2000 mg/L), solution pH (0.01 and 0.1 M acids) and three metabolic complexing agents (citrate, malate and lactate). It was shown that the adsorption of the various Ni- and Co-complexes on Purolite were quite low, 16-18 and 5.4-9 mg/g of resin, respectively, in comparison to the smaller nickel ions and nickel sulfate. This was attributed to the bulky organic ligands which promoted crowding effect or steric hindrance. The adsorption of these complexes was further hampered by the strong affinity of the resin to H+ ions under acidic conditions. Mechanisms of adsorption, as inferred from the fitted empirical Langmuir and Freundlich models, were correlated to the proposed steric hindrance and competitive adsorption effects. Nickel and cobalt elution from the resin were found be effective and were independent of the type of metal complexes and metal concentrations. This study demonstrated the relative challenges involved in recovering nickel and cobalt from bioleaching solutions.

  2. Docking of ethanamine Schiff base imines & metal (II) complexes, cytotoxicity & DNA interaction studies

    NASA Astrophysics Data System (ADS)

    Sujarani, S.; Ramu, A.

    2015-01-01

    The present study deals with a series of biologically and stereo chemically important novel transition metal (II) Schiff base chelates. The Cu (II), Co (II), Mn (II) and Ni (II) ions containing complexes were synthesized by using diphenylethanamine and 2-hydroxy/2, 4-dihydroxy/2-hydroxy-4-methoxybenzaldehydes. The synthesized complexes were characterized using micro analytical, IR, NMR, ESI-Mass, UV-Visible, cyclic voltammetry and the EPR spectroscopic techniques. The spectral data evidenced the action of ligands as a neutral bidentate Schiff bases, coordinating through azomethine nitrogen and oxygen atom of hydroxyl group. The interaction studies revealed the groove binding nature of complexes with CT-DNA. The ligand and synthesized metal complexes showed cytotoxicity against cancerous cells. The strong binding affinity of the imine and metal complexes was also confirmed by molecular docking studies.

  3. Prebiotic coordination chemistry: The potential role of transition-metal complexes in the chemical evolution

    NASA Technical Reports Server (NTRS)

    Beck, M.

    1979-01-01

    In approaching the extremely involved and complex problem of the origin of life, consideration of the coordination chemistry appeared not only as a possibility but as a necessity. The first model experiments appear to be promising because of prebiotic-type synthesis by means of transition-metal complexes. It is especially significant that in some instances various types of vitally important substances (nucleic bases, amino acids) are formed simultaneously. There is ground to hope that systematic studies in this field will clarify the role of transition-metal complexes in the organizatorial phase of chemical evolution. It is obvious that researchers working in the fields of the chemistry of cyano and carbonyl complexes, and of the catalytic effect of transition-metal complexes are best suited to study these aspects of the attractive and interesting problem of the origin of life.

  4. Design, synthesis, and biological properties of triazole derived compounds and their transition metal complexes.

    PubMed

    Chohan, Zahid H; Hanif, Muhammad

    2010-10-01

    Triazole derived Schiff bases and their metal complexes (cobalt(II), copper(II), nickel(II), and zinc(II)) have been prepared and characterized using IR, (1)H and (13)C NMR, mass spectrometry, magnetic susceptibility and conductivity measurements, and CHN analysis data. The structure of L(2), N-[(5-methylthiophen-2-yl)methylidene]-1H-1,2,4-triazol-3-amine, has also been determined by the X-ray diffraction method. All the metal(II) complexes showed octahedral geometry except the copper(II) complexes, which showed distorted octahedral geometry. The triazole ligands and their metal complexes have been screened for their in vitro antibacterial, antifungal, and cytotoxic activity. All the synthesized compounds showed moderate to significant antibacterial activity against one or more bacterial strains. It is revealed that all the synthesized complexes showed better activity than the ligands, due to coordination.

  5. Different coordination modes of 2-(diphenylphosphino)azobenzenes in complexation with hard and soft metals.

    PubMed

    Kano, Naokazu; Yamamura, Masaki; Meng, Xiangtai; Yasuzuka, Takaharu; Kawashima, Takayuki

    2012-10-07

    Control of coordination modes of a ligand in metal complexes is significant because the coordination modes influence catalytic properties of transition metal catalysts. Reactions of 2-diphenylphosphinoazobenzenes, which are in equilibrium with the inner phosphonium salts, with ZnCl(2), W(CO)(5)(THF), and PtCl(2)(cod) gave three different coordination types of metal complexes with distinctive UV-vis absorptions. All the complexes were characterized by X-ray crystallographic analyses. In the zinc and tungsten complexes, the source molecule functions as an amide ligand and a phosphine ligand, respectively. In the platinum complex, the phosphorus molecule works as a tridentate ligand with formation of a carbon-platinum bond.

  6. Complexities within distal sheet turbidite deposits: case study 160,000ka Icod Turbidite, Moroccan Turbidite System

    NASA Astrophysics Data System (ADS)

    Hunt, James; Wynn, Russell

    2010-05-01

    coarse silt or (2) removal of previously deposited silt by erosion of a post-depositional mudflow associated with mudcap remobilisation. Further to the stacked subunit facies and grain-size breaks, there are additional complexities to the deposit. An omission of a typical Bouma Ta facies is observed, replaced with a thick well-developed banded Bouma Tb, representing density sorting and flow fractionation of dense basaltic clasts and >100μm foraminifera. Above developing ripple laminations associated with Bouma Tc development is a 0.2-0.5m thick convolute laminated sand. This convoluted sand represents increasing shear stress across developing ripples. Grain-size analysis and ITRAX x-radiographs highlighted an additional process within the mudcaps of the Icod turbidite within the Agadir Basin. The mudcap thickens towards the base of incline from the Agadir Basin to the Selvage Islands. Within the cores with an over-thickened mudcap, the mudcap contained silt contortions. X-radiographs using ITRAX further displayed these contorted silts in the mudcaps. Grain-size analysis was used to confirm the presence of silt and poor sorting through the regions of contortions. These contorted muds have a debritic fabric, and could represent post-depositional remobilisation of the accumulative suspended clay fraction as a mudflow, as it was settling on a gradient and destabilising. This presentation will show the complexities present in even distal sheet turbidites, and that detailed multidisciplinary studies are required to unravel the mechanisms at work during their deposition. Pearce, T.J., & Jarvis I. 1992. Composition and provenance of turbidite sands: Late Quaternary, Madeira Abyssal Plain. Rothwell, R.G., Pearce, I., & Weaver, P.P.E. 1992. Late Quaternary evolution of the Madeira Abyssal Plain, Canary Basin, NE Atlantic. Basin Research, vol.4, no.2, p.103-131. Watts, A.B., & Masson, D.G. 1995. A giant landslide on the north flank of Tenerife, Canary Islands. Journal of

  7. Lability criteria for successive metal complexes in steady-state planar diffusion.

    PubMed

    Salvador, José; Puy, Jaume; Galceran, Josep; Cecília, Joan; Town, Raewyn M; van Leeuwen, Herman P

    2006-01-19

    The lability of sequential metal complexes, ML, ML2, ML3, ... , up to a general 1:n metal/ligand stoichiometric ratio is considered for the case of metal ions (M) being accumulated at a surface (analytical sensor or organism). The analytical solution for the steady-state diffusion of M within a sequential complexation scheme allows quantification of the contribution from the dissociation of all of the complex species to the metal flux through the so-called lability degree, xi. A lability degree for each sequential complexation step is also defined which, due to the sequential character of the complexation scheme, depends not only on the proper kinetic constants of the given complexation step but also on the kinetics of the previous ones. When all contributions from the complexes are diffusion limited, the system is fully labile and xi=1. To provide simple lability criteria, the reaction layer approximation is extended to specifically deal with this sequential complexation scheme, so that a reaction layer thickness is defined when the existence of one particular rate-limiting step is assumed. Expressions for the classical lability parameter, L, are formulated using the reaction layer approximation. The change of the lability of the system as the diffusion layer thickness is modified is analyzed in detail. The contribution of the complex flux reflects the evolution of the system from labile to inert as the thickness of the sensor is appropriately decreased.

  8. Synthesis and antimalarial activity of metal complexes of cross-bridged tetraazamacrocyclic ligands

    PubMed Central

    Hubin, Timothy J.; Amoyaw, Prince N. -A.; Roewe, Kimberly D.; Simpson, Natalie C.; Maples, Randall D.; Carder Freeman, TaRynn N.; Cain, Amy N.; Le, Justin G.; Archibald, Stephen J.; Khan, Shabana I.; Tekwani, Babu L.; Khan, M. O. Faruk

    2014-01-01

    Using transition metals such as manganese(II), iron(II), cobalt(II), nickel(II), copper(II), and zinc(II), several new metal complexes of cross-bridged tetraazamacrocyclic chelators namely, cyclen- and cyclam-analogs with benzyl groups, were synthesized and screened for in vitro antimalarial activity against chloroquine-resistant (W2) and chloroquine-sensitive (D6) strains of Plasmodium falciparum. The metal-free chelators tested showed little or no antimalarial activity. All the metal complexes of the dibenzyl cross-bridged cyclam ligand exhibited potent antimalarial activity. The Mn2+ complex of this ligand was the most potent with IC50s of 0.127 and 0.157 µM against the chloroquine-sensitive (D6) and chloroquine-resistant (W2) P. falciparum strains, respectively. In general, the dibenzyl hydrophobic ligands showed better antimalarial activity compared to the activity of monobenzyl ligands, potentially because of their higher lipophilicity and thus better cell penetration ability. The higher antimalarial activity displayed by the manganese complex for the cyclam ligand in comparison to that of the cyclen, correlates with the larger pocket of cyclam compared to that of cyclen which produces a more stable complex with the Mn2+. Few of the Cu2+ and Fe2+ complexes also showed improvement in activity but Ni2+, Co2+ and Zn2+ complexes did not show any improvement in activity upon the metal-free ligands for anti-malarial development. PMID:24857776

  9. Complexing sorbents with heterocyclic amino groups for concentrating platinum-group metals

    SciTech Connect

    Myasoedova, G.V.; Shcherbinina, N.I.; Komozin, P.N.

    1995-06-01

    Sorbents prepared on the basis of amines, in particular, those bearing heterocyclic amino groups and nitrogen-containing matrices, hold much promise for the sorptifve sepatration of platinum-group metals. The results of the study of new complexing sorbents based on 2,4,6-triamino-1,3,5-triazine (melamine) and bearing 3(5)-methylpyrazole, imidazole, and benzimidazole groups are presented in this work. The sorption and complexing properties of the sorbents with respect to platinum-group metals were studied. The possibility of using new sorbents for the group concentration of platinum-group metals was demonstrated.

  10. Relativistic effect on enthalpy of formation for transition-metal complexes

    NASA Astrophysics Data System (ADS)

    Nakajima, Yuya; Seino, Junji; Nakai, Hiromi

    2017-04-01

    This Letter examines the enthalpy of formation for 12 transition metal diatomic molecules and 23 transition metal complexes from the viewpoint of effect of the relativistic effect by using the infinite-order Douglas-Kroll-Hess method with the local unitary transformation and three types of pseudopotentials for several levels of theory. The spin-orbit effect contribution to the enthalpy of formation is more than 10 kcal/mol for third transition metal complexes. Frozen orbital approximation at the outermost orbitals in pseudopotential methods shows a contribution to the enthalpy of formation that is more than two times larger than those of inner core orbitals.

  11. Spectroscopic study of molecular structure, antioxidant activity and biological effects of metal hydroxyflavonol complexes

    NASA Astrophysics Data System (ADS)

    Samsonowicz, Mariola; Regulska, Ewa

    2017-02-01

    Flavonols with varied hydroxyl substitution can act as strong antioxidants. Thanks to their ability to chelate metals as well as to donate hydrogen atoms they have capacity to scavenge free radicals. Their metal complexes are often more active in comparison with free ligands. They exhibit interesting biological properties, e.g. anticancer, antiphlogistic and antibacterial. The relationship between molecular structure and their biological properties was intensively studied using spectroscopic methods (UV-Vis, IR, Raman, NMR, ESI-MS). The aim of this paper is review on spectroscopic analyses of molecular structure and biological activity of hydroxyflavonol metal complexes.

  12. Inherent structure length in metallic glasses: simplicity behind complexity

    PubMed Central

    Wu, Yuan; Wang, Hui; Cheng, Yongqiang; Liu, Xiongjun; Hui, Xidong; Nieh, Taigang; Wang, Yandong; Lu, Zhaoping

    2015-01-01

    One of the central themes in materials science is the structure-property relationship. In conventional crystalline metals, their mechanical behaviour is often dictated by well-defined structural defects such as dislocations, impurities, and twins. However, the structure-property relationship in amorphous alloys is far from being understood, due to great difficulties in characterizing and describing the disordered atomic-level structure. Herein, we report a universal, yet simple, correlation between the macroscopic mechanical properties (i.e., yield strength and shear modulus) and a unique characteristic structural length in metallic glasses (MGs). Our analysis indicates that this characteristic length can incorporate effects of both the inter-atomic distance and valence electron density in MGs, and result in the observed universal correlation. The current findings shed lights on the basic understanding of mechanical properties of MGs from their disordered atomic structures. PMID:26245801

  13. Inherent structure length in metallic glasses: Simplicity behind complexity

    DOE PAGES

    Wu, Yuan; Wang, Hui; Cheng, Yongqiang; ...

    2015-08-06

    One of the central themes in materials science is the structure-property relationship. In conventional crystalline metals, their mechanical behaviour is often dictated by well-defined structural defects such as dislocations, impurities, and twins. However, the structure-property relationship in amorphous alloys is far from being understood, due to great difficulties in characterizing and describing the disordered atomic-level structure. Here, we report a universal, yet simple, correlation between the macroscopic mechanical properties (i.e., yield strength and shear modulus) and a unique characteristic structural length in metallic glasses (MGs). Lastly, our analysis indicates that this characteristic length can incorporate effects of both the inter-atomicmore » distance and valence electron density in MGs, and result in the observed universal correlation. The current findings shed lights on the basic understanding of mechanical properties of MGs from their disordered atomic structures.« less

  14. Inherent structure length in metallic glasses: Simplicity behind complexity

    SciTech Connect

    Wu, Yuan; Wang, Hui; Cheng, Yongqiang; Liu, Xiongjun; Hui, Xidong; Nieh, Taigang; Wang, Yandong; Lu, Zhaoping

    2015-08-06

    One of the central themes in materials science is the structure-property relationship. In conventional crystalline metals, their mechanical behaviour is often dictated by well-defined structural defects such as dislocations, impurities, and twins. However, the structure-property relationship in amorphous alloys is far from being understood, due to great difficulties in characterizing and describing the disordered atomic-level structure. Here, we report a universal, yet simple, correlation between the macroscopic mechanical properties (i.e., yield strength and shear modulus) and a unique characteristic structural length in metallic glasses (MGs). Lastly, our analysis indicates that this characteristic length can incorporate effects of both the inter-atomic distance and valence electron density in MGs, and result in the observed universal correlation. The current findings shed lights on the basic understanding of mechanical properties of MGs from their disordered atomic structures.

  15. Cyclic voltammetry characterization of metal complex imprinted polymer.

    PubMed

    Zeng, Yi Ning; Zheng, Ning; Osborne, Peter G; Li, Yuan Zong; Chang, Wen Bao; Wen, Mei Juan

    2002-01-01

    Polymer capable of specific binding to Cu(2+)-2, 2'-dipyridyl complex was prepared by molecular imprinting technology. The binding specificity of the polymer to the template (Cu(2+)-2, 2'-dipyridyl complex) was investigated by cyclic voltammetric scanning using the carbon paste electrode modified by polymer particles in phosphate buffer solution. Factors that influence rebinding of the imprinted polymer were explored. The results demonstrated that cyclic voltammetry was an efficient approach to explore interactions between template and imprinted polymers.

  16. Cyclometalated complexes of platinum metals - the new luminescent sensors

    NASA Astrophysics Data System (ADS)

    Nikolaeva, M. V.; Katlenok, E. A.; Khakhalina, M. S.; Puzyk, M. V.; Balashev, K. P.

    2015-11-01

    The influence of the environment on the cyclometalated Pt(II), Pd(II), Ir(III) complexes' optical properties in the presence of various organic and inorganic compounds in solution and the gas phase is studied. The feasibility of complexes' using as optical sensors for molecular oxygen, halides ions, hydrogen and Hg(II) cations in the liquid phase, as well as for water and some organic solvents' vapor in the immobilized state in the MF-4SK membrane.

  17. One-step synthesis of nanocrystalline transition metal oxides on thin sheets of disordered graphitic carbon by oxidation of MXenes.

    PubMed

    Naguib, Michael; Mashtalir, Olha; Lukatskaya, Maria R; Dyatkin, Boris; Zhang, Chuanfang; Presser, Volker; Gogotsi, Yury; Barsoum, Michel W

    2014-07-18

    Herein we show that heating 2D Ti3C2 in air results in TiO2 nanocrystals enmeshed in thin sheets of disordered graphitic carbon structures that can handle extremely high cycling rates when tested as anodes in lithium ion batteries. Oxidation of 2D Ti3C2 in either CO2 or pressurized water also resulted in TiO2-C hybrid structures. Similarly, other hybrids can be produced, as we show here for Nb2O5/C from 2D Nb2C.

  18. On the material modelling of anisotropy, hardening and failure of sheet metals in the finite strain regime

    SciTech Connect

    Vladimirov, I. N.; Tini, V.; Kiliclar, Y.; Reese, S.

    2011-05-04

    In this paper, we discuss the application of a newly developed coupled material model of finite anisotropic multiplicative plasticity and continuum damage to the numerical prediction of the forming limit diagram at fracture (FLDF). The model incorporates Hill-type plastic anisotropy, nonlinear Armstrong-Frederick kinematic hardening and nonlinear isotropic hardening. The numerical examples examine the simulation of forming limit diagrams at fracture by means of the so-called Nakajima stretching test. Comparisons with experimental data for aluminium sheets show a good agreement with the finite element results.

  19. N-heterocyclic carbene metal complexes as bio-organometallic antimicrobial and anticancer drugs.

    PubMed

    Patil, Siddappa A; Patil, Shivaputra A; Patil, Renukadevi; Keri, Rangappa S; Budagumpi, Srinivasa; Balakrishna, Geetha R; Tacke, Matthias

    2015-01-01

    Late transition metal complexes that bear N-heterocyclic carbene (NHC) ligands have seen a speedy growth in their use as both, metal-based drug candidates and potentially active homogeneous catalysts in a plethora of C-C and C-N bond forming reactions. This review article focuses on the recent developments and advances in preparation and characterization of NHC-metal complexes (metal: silver, gold, copper, palladium, nickel and ruthenium) and their biomedical applications. Their design, syntheses and characterization have been reviewed and correlated to their antimicrobial and anticancer efficacies. All these initial discoveries help validate the great potential of NHC-metal derivatives as a class of effective antimicrobial and anticancer agents.

  20. Correlation between oxygen adsorption energy and electronic structure of transition metal macrocyclic complexes

    SciTech Connect

    Liu, Kexi; Lei, Yinkai; Wang, Guofeng

    2013-11-28

    Oxygen adsorption energy is directly relevant to the catalytic activity of electrocatalysts for oxygen reduction reaction (ORR). In this study, we established the correlation between the O{sub 2} adsorption energy and the electronic structure of transition metal macrocyclic complexes which exhibit activity for ORR. To this end, we have predicted the molecular and electronic structures of a series of transition metal macrocyclic complexes with planar N{sub 4} chelation, as well as the molecular and electronic structures for the O{sub 2} adsorption on these macrocyclic molecules, using the density functional theory calculation method. We found that the calculated adsorption energy of O{sub 2} on the transition metal macrocyclic complexes was linearly related to the average position (relative to the lowest unoccupied molecular orbital of the macrocyclic complexes) of the non-bonding d orbitals (d{sub z{sup 2}}, d{sub xy}, d{sub xz}, and d{sub yz}) which belong to the central transition metal atom. Importantly, our results suggest that varying the energy level of the non-bonding d orbitals through changing the central transition metal atom and/or peripheral ligand groups could be an effective way to tuning their O{sub 2} adsorption energy for enhancing the ORR activity of transition metal macrocyclic complex catalysts.