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. Twisting of sheet metals

    NASA Astrophysics Data System (ADS)

    Pham, C. H.; Thuillier, S.; Manach, P. Y.

    2013-12-01

    Twisting of metallic sheets is one particular mode of springback that occurs after drawing of elongated parts, i.e. with one dimension much larger than the two others. In this study, a dedicated device for drawing of elongated part with a U-shaped section has been designed on purpose, in order to obtain reproducible data. Very thin metallic sheet, of thickness 0.15 mm, has been used, so that the maximum length of the part is 100 mm. Two different orientations of the part with respect to the tools have been chosen: either aligned with the tools, or purposefully misaligned by 2°. Several samples were drawn for each configuration, leading to the conclusion that almost no twisting occurs in the first case whereas a significant one can be measured for the second one. In a second step, 2D and 3D numerical simulations within the implicit framework for drawing and springback were carried out. A mixed hardening law associated to von Mises yield criterion represents accurately the mechanical behavior of the material. This paper highlights a comparison of numerical predictions with experiments, e.g. the final shape of the part and the twisting parameter.

  4. 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.

  5. 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.

  6. 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.

  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: 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.

  9. Metals fact sheet - lanthanum

    SciTech Connect

    1995-04-01

    Mosander was the first to extract the elusive rare earth, lanthanum, from unrefined cerium nitrate in 1839. The name was derived from the Greek word lanthanein, meaning {open_quotes}to escape notice.{close_quotes} Lanthanum is the lightest rare earth and a very malleable metal-soft enough to be cut with a knife. Used primarily as an additive in steels and non-ferrous metals, lanthanum is the lightest rare earth element and one of four rare earths from which mischmetal is made. Additional applications include advanced batteries, optical fibers, and phosphors.

  10. Metals fact sheet - indium

    SciTech Connect

    1994-01-01

    Indium is generally found in concentrations averaging 10 to 20 ppm in sphalerite and chalcopyrite ores associated with zinc, copper, lead and tin deposits. Indium is recovered as a by-product of base metal mining by open pit, underground and other methods. After the recovery of zinc by the electrolytic process (copper concentrate by flotation, and lead and tin by electrolysis), indium antimonide slimes left on the anode and the indium-containing spent electrolyte become the input material for the processing of indium. Sulfuric acid is combined with the residues and heated to form sulfates which are then leached with water to filter off the remaining tin, lead and antimony. The indium in solution is recovered by cementation on aluminum, washed, melted, and refined into a metal.

  11. 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…

  12. 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.

  13. 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.

  14. 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…

  15. Reinforcement for Stretch Formed Sheet Metal

    NASA Technical Reports Server (NTRS)

    Lea, J. B.; Baxter, C. R.

    1983-01-01

    Tearing of aluminum sheet metal durinng stretch forming prevented by flame spraying layer of aluminum on edges held in stretch-forming machine. Technique improves grip of machine on metal and reinforced sheet better able to with stand concentration of force in vicinity of grips.

  16. 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.

  17. Electromagnetic augmentation for casting of thin metal sheets

    SciTech Connect

    Hull, J.R.

    1989-07-11

    This patent describes an apparatus for the horizontal casting of thin metal sheets. The apparatus consists of: vessel means containing a molten metal and including an aperture for discharging the molten metal in the form of a thin horizontal sheet; mold means for receiving, confining and directing the molten metal sheet and for removing heat from the molten metal sheet in effecting the solidification thereof; electromagnetic conducting means including a DC conductor disposed about the metal sheet for directing a DC magnetic field along the direction of displacement of and about the metal sheet; and a DC voltage source coupled to the metal sheet for establishing a direct current therein, such that the direct current interacts with the DC magnetic field for generating and exerting a constant uniform levitation force on the metal sheet wherein the pressure exerted by the metal sheet upon the mold means is reduced to zero.

  18. 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

  19. 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.

  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. 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.

  2. 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.

  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. Advances in characterization of sheet metal forming limits

    NASA Astrophysics Data System (ADS)

    Stoughton, Thomas B.; Carsley, John E.; Min, Junying; Lin, Jianping

    2016-08-01

    This paper accounts for nonlinear strain path, sheet curvature, and sheet-tool contact pressure to explain the differences in measured forming limit curves (FLCs) obtained by Marciniak and Nakajima Tests. While many engineers working in the sheet metal forming industry use the raw data from one or the other of these tests without consideration that they reflect the convolution of material properties with the complex processing conditions involved in these two tests, the method described in this paper has the objective to obtain a single FLC for onset of necking for perfectly linear strain paths in the absence of through-thickness pressure and restricted to purely in-plane stretching conditions, which is proposed to reflect a true material property. The validity of the result is checked using a more severe test in which the magnitude of the nonlinearity, curvature, and pressure are doubled those involved in the Nakajima Test.

  5. 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…

  6. 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

  7. Sheet metal hydroforming of functional composite structures

    NASA Astrophysics Data System (ADS)

    Ibis, M.; Griesheimer, S.; Salun, L.; Rausch, J.; Groche, P.

    2011-03-01

    This paper studies the formability of functional composite structures, consisting of a metal substrate, insulating plastic foils, flat copper conductors and printable conductive polymers. The aim is the production of smart components in a sheet metal hydroforming process. In addition to their mechanical properties, these components can also transfer energy and data. Conventional boundaries between mechanics and electronics will be relaxed expediently. The challenge of this study is the design of the forming process, so that all elements of the multi-layer composites will withstand the process conditions. In this context, an analytical method for estimating the formability of these smart components is presented. The main objectives are the definition of basic failure modes and the depiction of the process limits.

  8. 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.

  9. 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.

  10. Explosive force of primacord grid forms large sheet metal parts

    NASA Technical Reports Server (NTRS)

    1966-01-01

    Primacord which is woven through fish netting in a grid pattern is used for explosive forming of large sheet metal parts. The explosive force generated by the primacord detonation is uniformly distributed over the entire surface of the sheet metal workpiece.

  11. 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

  12. 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,…

  13. 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

  14. 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

  15. 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

  16. Noble metal chain adsorption on graphene sheet

    NASA Astrophysics Data System (ADS)

    Salehi, Hamdollah; Moaddeli, Mohammad; Amiri, Peiman

    2016-05-01

    Van-der-Waals dispersion force plays a crucial role in physisorption mechanisms. Using density functional theory, the adsorption of noble metal (Cu, Ag, and Au) chains on graphene sheet was studied within two possible adsorption geometries, the zig-zag and the preferred armchair one. In order to take the portion of non-local correlations into account, we applied both semi-empirical and ab-initio van-der-Waals functionals in our calculations. The interaction leads to a charge transfer at the physisorption interface and makes graphene p-doped. Not only does the Fermi level shifts with respect to the Dirac point, but also a small band gap opening is predicted. Work function calculations confirm the presence of physisorption mechanism at the interface.

  17. 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.

  18. Studies in Cup Drawing Behavior of Polymer Laminated Sheet Metal

    NASA Astrophysics Data System (ADS)

    Elnagmi, M.; Jain, M.; Bruhis, M.; Nielsen, K.

    2011-08-01

    Axisymmetric deep drawing behavior of a polymer laminated sheet metal (PLSM) is investigated using an axisymmetric cup drawing test. PLSMs are of interest as a replacement for painted finishes for automotive applications as they have the potential to achieve good quality long lasting and aesthetically appealing surfaces on stamped parts. However, there is limited understanding of PLSMs in automotive deep drawing situations to produce complex 3-D parts. The tests are carried out using well-controlled, laboratory-based, dual-action, servo-hydraulic forming presses under blank-holder force and punch displacement control conditions. An optical strain mapping system is used to measure the surface strains (and to construct 3D strain maps) from the film side of the deformed samples for a range of forming conditions. Deep drawing characteristics such as punch load versus punch displacement traces, strain distribution along the cup profile, flange wrinkling and fracture characteristics are experimentally assessed for stainless steel-plastic film laminated sheet materials. Also the effect of lamination pressure on wrinkling and delamination is investigated for a decorative pressure sensitive adhesive film affixed to the stainless steel sheet.

  19. 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.

  20. 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

  1. 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)

  2. Investigation Of Tailored Blank Production By The Process Class Sheet-Bulk Metal Forming

    NASA Astrophysics Data System (ADS)

    Merklein, M.; Opel, S.

    2011-01-01

    Nowadays efforts are made to improve sheet metal manufacturing processes and forming capability. Functional sheet metal components, for example toothed synchronizer rings, show closely-tolerated complex geometric features, especially in the automotive industry. Unfortunately sheet metal forming operations do not offer the possibility for complex shapes as do for example cutting technologies [1]. To avoid this restriction, the usage of semi-finished products with a material pre-distribution in the blank is investigated. So-called tailored blanks are usually made of different materials or sheet thicknesses. A common way of joining diverse blanks is welding [2]. In most cases the joining has a significant influence on the consecutively forming process due to varying local mechanical properties [3]. Hence the manufacturing of tailored blanks with a defined sheet thickness characteristic by the process class "sheet-bulk metal forming" is investigated. Subsequent the tailored blanks are provided for forming operations such as deep-drawing and the direct forming of complex functional shape elements. Aim of the project is the manufacturing of circular blanks with a sheet thickening in the exterior area by an upsetting operation. At the beginning, FE-based studies and physical experiments using blanks of DC04 are carried out, to create a fundamental knowledge base of the forming process. A comparatively large contact area between blank and forming tool, a three-dimensional material flow and the low sheet thickness cause high process forces. Building up a multi-stage upsetting process with different sequenced tool geometries is one approach to meet this challenge. The material flow out of the sheet center is realized step-by-step to lower the actual contact area and sequential the appearing forces.

  3. Selenophene transition metal complexes

    SciTech Connect

    White, C.J.

    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 {eta}{sup 5}- and the {eta}{sup 1}(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 {sup 77}Se 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 {eta}{sup 1}(S)-bound thiophenes, {eta}{sup 1}(S)-benzothiophene and {eta}{sup 1}(Se)-bound selenophenes has been demonstrated. The deprotonation and rearrangement of the {eta}{sup 1}(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)(PPh{sub 3})Re(2-benzothioenylcarbene)]O{sub 3}SCF{sub 3} 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 {eta}{sup 1}(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.

  4. New Modelling of Localized Necking in Sheet Metal Stretching

    NASA Astrophysics Data System (ADS)

    Bressan, José Divo

    2011-01-01

    Present work examines a new mathematical model to predict the onset of localized necking in the industrial processes of sheet metal forming such as biaxial stretching. Sheet metal formability is usually assessed experimentally by testing such as the Nakajima test to obtain the Forming Limit Curve, FLC, which is an essential material parameter necessary to numerical simulations by FEM. The Forming Limit Diagram or "Forming Principal Strain Map" shows the experimental FLC which is the plot of principal true strains in the sheet metal surface, ɛ1 and ɛ2, occurring at critical points obtained in laboratory formability tests or in the fabrication process. Two types of undesirable rupture mechanisms can occur in sheet metal forming products: localized necking and shear induced fracture. Therefore, two kinds of limit strain curves can be plotted: the local necking limit curve FLC-N and the shear fracture limit curve FLC-S. Localized necking is theoretically anticipated to initiate at a thickness defect ƒin = hib/hia inside the grooved sheet thickness hia, but only at the instability point of maximum load. The inception of grooving on the sheet surface evolves from instability point to localized necking and final rupture, during further sheet metal straining. Work hardening law is defined for a strain and strain rate material by the effective stress σ¯ = σo(1+βɛ¯)n???ɛM. The average experimental hardening law curve for tensile tests at 0°, 45° and 90°, assuming isotropic plasticity, was used to analyze the plasticity behavior during the biaxial stretching of sheet metals. Theoretical predicted curves of local necking limits are plotted in the positive quadrant of FPSM for different defect values ƒin and plasticity parameters. Limit strains are obtained from a software developed by the author. Some experimental results of forming limit curve obtained from experiments for IF steel sheets are compared with the theoretical predicted curves: the correlation is

  5. Direct evidence of metallic bands in a monolayer boron sheet

    NASA Astrophysics Data System (ADS)

    Feng, Baojie; Zhang, Jin; Liu, Ro-Ya; Iimori, Takushi; Lian, Chao; Li, Hui; Chen, Lan; Wu, Kehui; Meng, Sheng; Komori, Fumio; Matsuda, Iwao

    2016-07-01

    The search for metallic boron allotropes has attracted great attention in the past decades and recent theoretical works predict the existence of metallicity in monolayer boron. Here, we synthesize the β12-sheet monolayer boron on a Ag(111) surface and confirm the presence of metallic boron-derived bands using angle-resolved photoemission spectroscopy. The Fermi surface is composed of one electron pocket at the S ¯ point and a pair of hole pockets near the X ¯ point, which is supported by the first-principles calculations. The metallic boron allotrope in β12 sheet opens the way to novel physics and chemistry in material science.

  6. First pentahaptofullerene metal complexes

    SciTech Connect

    Masaya, Sawamura; Iikura, Hitoshi; Nakamura, Eiichi

    1996-12-18

    Cyclopentadienyl metal complexes have played important roles in chemistry owing to their unique structures and functional activities. Here we report the synthesis and characterization of an entirely new class of cyclopentadienyl (Cp) metal complexes ({eta}{sup 5}-C{sub 60}Ph{sub 5})MLn (MLn = Li, K, Tl, and Cu.PEt{sub 3}). In these molecules, the five Cp carbons represent one pentagon of C{sub 60}, isolated from the remaining 50 sp{sup 2} carbon atoms by five surrounding sp{sup 3} carbon atoms each bearing a phenyl group. The X-ray crystal structure analysis of the thallium complex Tl({eta}{sup 5}-C{sub 60}Ph{sub 5}).2.5THF revealed its unique and esthetically pleasing C{sub 5} symmetrical molecular structure with the phenyl groups forming a chiral propeller array. The thallium atom is deeply buried in the cavity created by the phenyl groups, bonding to the five Cp carbons ({eta}{sup 5}-coordination) with an averaged Tl-C distance of 2.87 A. The key finding that we made in this research was a remarkable 5-fold addition of an organocopper reagent to C{sub 60}, which stands in contrast to the monoaddition reaction of Grignard or organolithium reagents. 10 refs., 1 fig.

  7. Joining of Thin Metal Sheets by Shot Peening

    NASA Astrophysics Data System (ADS)

    Harada, Yasunori

    2011-01-01

    In shot peening the substrate undergoes large plastic deformation near the surface due to the hit with shots. The plastic flow areas formed by cold working may form the surface layer. Authors have recently proposed new joining methods using shot peening, shot lining and shot caulking. Our approach has been applied to the butt joining of the dissimilar metal sheets. In the present study, joining of thin metal sheets using a shot peening process was investigated to improve the joinability. In the joined section, the edge of sheets is the equally-spaced slits. In this method, the convex edges of the sheet are laid on top of the other sheet. Namely, the two sheets are superimposed in the joining area. When the connection is shot-peened, the material of the convex area undergoes large plastic deformation near the surface due to the collision of shots. In this process, particularly noteworthy is the plastic flow near surface layer. The convex edges of the sheet can be joined to the other sheet, thus two sheets are joined each other. In the experiment, the shot peening treatment was performed by using an air-type peening machine. The shots used were made of high carbon cast steel. Air pressure was 0.6 MPa and peening time was in the range of 30-150s. The peening conditions were controlled in the experiment. The thin sheets were commercial low-carbon steel, stainless steel, pure aluminum, and aluminium alloy. The effects of processing conditions on the joinability were mainly examined. The joint strength increased with the kinetic energy of shots. It was found that the present method was effective for joining of thin metal sheets.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

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

    PubMed

    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.

  14. 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.

  15. Laser-Assisted Sheet Metal Working of High Strength Steels in Serial Production

    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 need to save energy and a responsible use of natural resources. The high strength and the low ductility restricts using state of art technology to sheer, bend, emboss or deep draw parts with the needed complexity and quality. The Fraunhofer IPT developed a combination of laser-assisted preheating and conventional punching to a new hybrid technology which allows to shear, bend, emboss and draw high strength materials with a high quality and complexity in a serial production.

  16. 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.

  17. 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…

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

    ERIC Educational Resources Information Center

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

    This competency-based curriculum guide on the specialty area of sheet metal is part of the Introduction to Construction series. The series is designed with the flexible training requirements of open shop contractors, preapprenticeship programs, multicraft high school programs, technology education programs, and cooperative education programs in…

  19. 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

  20. Ductile damage prediction in sheet and bulk metal forming

    NASA Astrophysics Data System (ADS)

    Badreddine, Houssem; Labergère, Carl; Saanouni, Khemais

    2016-04-01

    This paper is dedicated to the presentation of an advanced 3D numerical methodology for virtual sheet and/or bulk metal forming simulation to predict the anisotropic ductile defects occurrence. First, the detailed formulation of thermodynamically-consistent fully coupled and fully anisotropic constitutive equations is given. The proposed constitutive equations account for the main material nonlinearities as the anisotropic plastic flow, the mixed isotropic and kinematic hardening and the anisotropic ductile damage under large inelastic strains. Second, the related numerical aspects required to solve the initial and boundary value problem (IBVP) are very briefly presented in the framework of the 3D finite element method. The global resolution schemes as well as the local integration schemes of the fully coupled constitutive equations are briefly discussed. Finally, some typical examples of sheet and bulk metal forming processes are numerically simulated using the proposed numerical methodology.

  1. 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.

  2. Complexity in `simple' metals

    NASA Astrophysics Data System (ADS)

    Rousseau, Bruno; Ashcroft, Neil W.

    2008-03-01

    In electronic and structural terms, the light alkalis have long been regarded as `simple systems', at least under ordinary conditions. However, when compressed they exhibit unforeseen complexity; the melting curve of sodium, for example, has a striking maximum, falling to near room temperature melting where a complex structure (CI16) is found, this being in the cubic class but with 16 atoms per unit cell [1,2]. The light alkalis have been extensively studied using ab initio methods with standard assumptions of transferability made for the key pseudopotential input information, largely atomic based. Lacking still, however, is a somewhat more intuitive and physical understanding of the developments in electronic structure with progressive increase in density. In the present work, the problem is treated with non-linear response theory and non-overlapping pseudopotentials, and the structural complexity traced to effective ion-ion interactions with features that both at short range and long display competing state dependence. [1] Gregoryanz et al., Phys. Rev. Lett. 94, 185502 (2005) [2] McMahon et al., Chem. Soc. Rev. 35, 943 (2006)

  3. Thermographic imaging of cracks in thin metal sheets

    NASA Technical Reports Server (NTRS)

    Cramer, K. E.; Winfree, William P.; Howell, Patricia A.; Syed, Hazari; Renouard, Keith A.

    1992-01-01

    The presence of cracks significantly decreases the structural integrity of thin metal sheets used in aerospace applications. Thermographic detection of surface temperature variations due to these cracks is possible after external heating. An approximate line source of heat is used to produce an inplane flow of heat in the sheet. A crack in the sheet perturbs the inplane flow of heat and can be seen in an image of the surface temperature of the sheet. An effective technique for locating these perturbations is presented which reduces the surface temperature image to an image of variations in the inplane heat flow. This technique is shown to greatly increase the detectability of the cracks. This thermographic method has advantages over other techniques in that it is able to remotely inspect a large area in a short period of time. The effectiveness of this technique depends on the shape, position and orientation of the heat source with respect to the cracks as well as the extent to which the crack perturbs the surface heat flow. The relationship between these parameters and the variation in the heat flow is determined both by experimental and computational techniques. Experimental data is presented for through-the-thickness, subsurface and surface EDM notches. Data for through-the-thickness fatigue cracks are also presented.

  4. Sectional Finite Element Analysis on Viscous Pressure Forming of Sheet Metal

    NASA Astrophysics Data System (ADS)

    Liu, Jianguang; Wang, Zhongjin; Liu, Yan

    2007-05-01

    Viscous pressure forming (VPF) is a recently developed sheet flexible-die forming process, which uses a kind of semi-solid, flowable and viscous material as pressure-carrying medium that typically applied on one side of the sheet metal or on both sides of sheet metal. Different from traditional sheet metal forming processes in which sheet metal is the unique deformation-body, VPF is a coupling process of visco-elastoplastic bulk deformation of viscous medium and elasto-plastic deformation of sheet metal. A sectional finite element model for the coupled deformation between visco-elastoplastic body and elasto-plastic sheet metal was proposed to analyze VPF. The resolution of the Updated Lagrangian formulation is based on a static approach. By using static-explicit time integration strategy, the deformation of elasto-plastic sheet metal and visco-elastoplastic body can keep stable. The frictional contact between sheet metal and visco-elastoplastic body is treated by penalty function method. Using the proposed algorithm, sheet metal viscous pressure bulging (VPB) process is analyzed and compared with experiments. A good agreement between numerical simulation results and experimental ones proved the efficiency and stability of this algorithm.

  5. 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

  6. 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

  7. 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.

  8. Fast numerical simulation of sheet metal forming using the program QuickForm

    NASA Astrophysics Data System (ADS)

    Bao, Yidong; Chen, Junwei; Wang, Zhiguo; Chen, Wenliang; Lee, Wing

    2010-06-01

    The fast numerical simulation system QuickForm has been self-developed specially for sheet metal forming with complex geometries. In order to resolve the convergence problem of static implicit method due to the change of contact state, the uncoupling solution method of the non-linear differential equations is used in QucikForm program. The bending effect and drawing effect during forming procedure are treated into two separate processes in QuickForm system, so this uncoupling solution has two basic steps. Firstly an approximate method named pre-stressed membrane element is used to achieve the intermediate configuration of sheet in this incremental step before incremental step iteration. The sheet shape of intermediate configuration depends on the current tooling position. Secondly the nonlinear material flow within this intermediate configuration is carried out, which means the nodes of deformed sheet can only slide on this form. The highly efficient iterative solver can be used to the solution of linear equations since the improved conditioning of the linear equations resulting from the uncoupling solution. Numerical simulation results of complex parts demonstrate the higher efficiency and accuracy of the proposed special purpose program.

  9. 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.

  10. On the mechanics of localized necking in anisotropic sheet metals

    NASA Astrophysics Data System (ADS)

    Hill, R.

    2001-09-01

    The ductility of sheet metals formed by cold rolling is often assessed by tension tests on long rectangular strips which are cut from a sheet at various angles to the direction of rolling. A strip typically deforms homogeneously to begin with, but eventually fails at a site where a narrow neck develops along a line that crosses the gauge section obliquely from side to side. The degree of obliquity depends on the material as well as on the cutting angle; so also does the stage of deformation at which a neck first appears. It has long been evident that material orthotropy and progressive hardening are crucial factors, but a theoretical analysis of the phenomenon that takes due account of both of these is apparently still lacking. Their joint influence is investigated here on the basis of the classical rigid/plastic constitutive model in its original form. Some pragmatic notions which were added later are excluded as being too simplistic and unnecessarily restrictive. The present analysis has been deliberately freed from ad hoc empiricism of any kind with a view to more realistic modeling in the future. Other than basic analytic requirements, there are no theoretical limitations on the path dependences of orthotropic parameters and the rate of strain hardening, nor on the evolving geometries of subsequent yield surfaces. It appears to the writer that, with well planned experiments and improved instrumentation, strip tests could be much more effective as a means to investigate orthotropic behaviour in metals.

  11. Lower Restrictions for Sheet Metal Trimming Processes can Reduce Die Costs in The Automotive Industry

    NASA Astrophysics Data System (ADS)

    Hogg, Markus; Rohleder, Martin; Roll, Karl

    2011-05-01

    To reduce costs of trimming dies influencing parameters of the shearing process were identified, new technical approaches for a more cost efficient die design were developed, and comprehensive investigations on a sample tool were done. These approaches will be verified on a trimming die in series production. If this pilot application is successful, many sheet metal forming parts can be trimmed by less die investment in the future. In the automotive industry complex sheet metal forming parts are often trimmed by shearing. Ideally this shearing is done with a 90° angle between the cutting edge and the part surface. Because of complex part geometry different angles always occur. Often shearing angles and the effective sheet thickness increases so much that trimming in the working direction of the press machine is not possible anymore. In these cases sliding cams have to be used. That makes trimming dies expensive and maintenance intensive. For reliable trimming a good understanding of the process and its limitations is necessary. By not considering these limitations the tool can fail after a few operations or/and the resulting edge of the sheet metal part is no longer acceptable. In worst case a new tool has to be built or at least must be reworked. In operational practice so far only empirical values about limitations are known. The stability limit for trimming is not known for all shearing angles and for new high-strength materials. Therefore detailed investigations were done on a sample tool to determine these stability limits for different materials and shearing angles. The basis for starting these principle investigations was empirical values from operational practise. By using a high-quality material and a completely new shape for the trimming die elements both the reliable processable effective sheet thickness respectively the shearing angle as well as the acting forces could be optimized. In the basic investigations trimming in one direction was often still

  12. 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.

  13. 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.

  14. Stabilization of ultrafine metal nanocatalysts on thin carbon sheets.

    PubMed

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

    2015-11-21

    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.

  15. Automotive Body Sheet Metal Maintenance I; Automotive Body Repair and Refinishing 1: 9033.05.

    ERIC Educational Resources Information Center

    Dade County Public Schools, Miami, FL.

    The automotive body sheet metal maintenance course is an exploratory course in the use of all sheet metal working and equipment common to this trade area. Included are techniques of diagnosis of damage and repair. Emphasized is the proper use of tools and fabrication methods used in automotive body maintenance and repair. This nine week course…

  16. 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.

  17. 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.

  18. Flat sheet metal girders with very thin metal web. Part I : general theories and assumptions

    NASA Technical Reports Server (NTRS)

    Wagner, Herbert

    1931-01-01

    The object of this report was to develop the structural method of sheet metal girders and should for that reason be considered solely from this standpoint. The ensuing methods were based on the assumption of the infinitely low stiffness in bending of the metal web. This simplifies the basis of calculations to such an extent that many questions of great practical importance can be examined which otherwise cannot be included in any analysis of the bending stiffness of the buckled plate. This report refers to such points as the safety in buckling of uprights to the effect of bending flexibility of spars, to spars not set parallel, etc.

  19. Numerical Simulation on Sheet Metal Forming with Rate-independent Polycrystalline Plasticity FEM

    NASA Astrophysics Data System (ADS)

    Zhang, Shaorui; Li, Dayong; Peng, Yinghong

    2004-06-01

    It has long been found that, during deformation process, the crystal orientations would gradually rotate around some ideal orientations, and then would affect the later deformation properties of sheet metal. So it is very important to introduce texture model into metal forming processes. In this paper, a rate-independent polycrystalline plasticity model is developed and introduced into dynamic explicit element method. Metal flow is assumed to occur by crystallographic slip on given slip systems within each crystal. Every integration point represents a single crystal. Then cup drawing of sheet metal is studied using crystalline plasticity finite element analysis. For the rolled aluminum sheet, which contains strong {001}<110> texture, earing is formed at 45° direction after cup drawing. For the annealing aluminum sheet, due to the balance between two main textures, the flange earing tendency is not obvious. And for the soft steel sheet with a faintish orientation distribution, the flange earing tendency is not obvious, too.

  20. 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".

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

    NASA Astrophysics Data System (ADS)

    Schikorra, Marco; Brosius, Alexander; Kleiner, Matthias

    2005-08-01

    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.

  2. High-speed laser cutting of thin metal sheets

    NASA Astrophysics Data System (ADS)

    Preissig, Kai-Uwe; Petring, Dirk; Herziger, Gerd

    1994-09-01

    Increasing productivity in splitting up of metal sheets by means of mechanical cutting processes is today limited by long change-over times as well as nonproductive times and insufficient quality caused by tool wear. In the case of high-quality materials even a slight quality reduction concerning development of dross attachment and induced stress leads to a lot of rejects. In order to increase the cutting speeds within a range economical for industrial use, i.e. about 100 m/min, a completely new type of laser cutting process had to be developed. As opposed to conventional laser cutting, during which a semicylindric cutting front is formed, a closed keyhole with subsequent melt film ejection is produced during the completely new laser cutting process. The incoupling of energy no longer only results from pure surface absorption but in addition from plasma formation and multiple reflection. With the help of the wear resisting tool `laser' the cutting quality is constantly good and can even be significantly improved in comparison with the conventional cutting method with circular knifes. In the case of a sheet thickness of 0.2 mm grain oriented electrical steel can be cut e.g. with a cutting speed of 130 m/min, aluminum with 270 m/min, copper with 95 m/min and zinc with 280 m/min; the necessary laser power is 1300 W. Based on the results of basic research the prototype of a laser slitting line was constructed and went into operation in autumn 1991. Up to now various materials for different customers have been cut on this slitting line and used in industry. Especially when cutting grain oriented electrical steel, which is a material with very high requirements on the cutting process, it becomes evident that the laser cutting process compared with the conventional technique has considerable advantages concerning cutting quality and quality assurance.

  3. Determination of forming limits of sheet metals by speckle interferometry

    NASA Astrophysics Data System (ADS)

    Vial-Edwards, C.; Guelorget, B.; Francois, Manuel; Lira, Ignacio; M'nzenmayer, M.

    2005-02-01

    Forming Limit Diagrams (FLD"s) can be defined by the criteria of either diffuse or localized necks. We used Electronic Speckle Pattern Interferometry (ESPI) in commercial 1100 aluminum sheet metals annealed at 400°C to determine the strains at which both types of neck started in uniaxial tension (U) and in quasi plane strain tension (PS) tests. In biaxial (B) loading we observed only the localized neck, but we were also able to detect a small defective spot at which fracture was incubated. The strains that produced the diffuse neck and the defective spot were approximately comparable to those predicted by Swift"s criterion for plastic instability. The difference between the FLD defined by a diffuse neck or by a defective spot leading to fracture and the one defined by a localized neck was found to be very noticeable in the U tests and less important, but still significant, in the PS and B tests. We found also that maximum load occurred at some point within the diffuse neck region and that afterwards the load carrying capacity was still substantial. We thus conclude that the decision on the criterion to use should be based on parts quality, safety and costs.

  4. Tailored work hardening descriptions in simulation of sheet metal forming

    NASA Astrophysics Data System (ADS)

    Vegter, Henk; Mulder, Hans.; van Liempt, Peter; Heijne, Jan

    2013-12-01

    In the previous decades much attention has been given on an accurate material description, especially for simulations at the design stage of new models in the automotive industry. Improvements lead to shorter design times and a better tailored use of material. It also contributed to the design and optimization of new materials. The current description of plastic material behaviour in simulation models of sheet metal forming is covered by a hardening curve and a yield surface. In this paper the focus will be on modelling of work hardening for advanced high strength steels considering the requirements of present applications. Nowadays work hardening models need to include the effect of hard phases in a soft matrix and the effect of strain rate and temperature on work hardening. Most material tests to characterize work hardening are only applicable to low strains whereas many practical applications require hardening data at relatively high strains. Therefore, physically based hardening descriptions are needed allowing reliable extensions to high strain values.

  5. 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.

  6. Optimization of Forming Processes with Different Sheet Metal Alloys

    NASA Astrophysics Data System (ADS)

    Sousa, Luísa C.; Castro, Catarina F.; António, Carlos C.

    2007-05-01

    Over the past decades relatively heavy components made of steel alloys comprise the majority of many manufactured parts due to steel's low cost, high formability and good strength. The desire to produce lightweight parts has led to studies searching for lighter and stronger materials such as aluminum alloys. However, they exhibit lower elastic stiffness than steel resulting in higher elastic strains causing known distortions such as spring-back and so decreasing accuracy of manufactured net-shape components. This paper presents a developed computational method to optimize the design of sheet metal processes using genetic algorithms. An inverse approach is considered so that the final geometry of the bended blank closely follows a prescribed one. The developed computational method couples a finite element forming simulation and an evolutionary algorithm searching the optimal design parameters of the process. The developed method searches the optimal parameters that ensure a perfect net-shape part. Different aluminum alloys candidates for automotive structural applications are considered and the optimal solutions are analyzed.

  7. Optimization of Forming Processes with Different Sheet Metal Alloys

    SciTech Connect

    Sousa, Luisa C.; Castro, Catarina F.; Antonio, Carlos C.

    2007-05-17

    Over the past decades relatively heavy components made of steel alloys comprise the majority of many manufactured parts due to steel's low cost, high formability and good strength. The desire to produce lightweight parts has led to studies searching for lighter and stronger materials such as aluminum alloys. However, they exhibit lower elastic stiffness than steel resulting in higher elastic strains causing known distortions such as spring-back and so decreasing accuracy of manufactured net-shape components. This paper presents a developed computational method to optimize the design of sheet metal processes using genetic algorithms. An inverse approach is considered so that the final geometry of the bended blank closely follows a prescribed one. The developed computational method couples a finite element forming simulation and an evolutionary algorithm searching the optimal design parameters of the process. The developed method searches the optimal parameters that ensure a perfect net-shape part. Different aluminum alloys candidates for automotive structural applications are considered and the optimal solutions are analyzed.

  8. 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.

  9. 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.

  10. 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

    2016-01-01

    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

  11. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

    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.

  13. 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.

  14. 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.

  15. Metal-metal multiply bonded complexes of technetium. Final report

    SciTech Connect

    Cotton, F.A.; Haefner, S.C.

    1995-03-30

    The primary objective of this project was to explore and develop the area of technetium metal-metal multiple bond chemistry. At the outset of the project, examples of metal-metal multiply bonded complexes of technetium were primarily limited to those supported by halide and carboxylate ligands. As a result, we intended to significantly expand the number of complexes containing Tc-Tc multiple bonds using ligands other than carboxylates or halides. In order to achieve this goal, the results obtained from years of dirhenium research was used as a guide for the development of new technetium compounds. Our emphasis, however, was on pursuing unanticipated results and exploiting the inherent differences between technetium and rhenium in order to develop chemistry beyond that which exists for rhenium. We have focused our attention on the preparation of dinuclear complexes with ligand sets that are known to support dinuclear metal-metal bonded cores in a variety of different metal oxidation states. Investigation of the consequences of electron addition and removal from metal-metal bonding manifold on the structural and physical properties of such dinuclear species will provide vital information regarding the electronic structure of Tc-Tc multiply bonded compounds.

  16. Programming complex shapes in thin nematic elastomer and glass sheets.

    PubMed

    Plucinsky, Paul; Lemm, Marius; Bhattacharya, Kaushik

    2016-07-01

    Nematic elastomers and glasses are solids that display spontaneous distortion under external stimuli. Recent advances in the synthesis of sheets with controlled heterogeneities have enabled their actuation into nontrivial shapes with unprecedented energy density. Thus, these have emerged as powerful candidates for soft actuators. To further this potential, we introduce the key metric constraint which governs shape-changing actuation in these sheets. We then highlight the richness of shapes amenable to this constraint through two broad classes of examples which we term nonisometric origami and lifted surfaces. Finally, we comment on the derivation of the metric constraint, which arises from energy minimization in the interplay of stretching, bending, and heterogeneity in these sheets. PMID:27575067

  17. Programming complex shapes in thin nematic elastomer and glass sheets

    NASA Astrophysics Data System (ADS)

    Plucinsky, Paul; Lemm, Marius; Bhattacharya, Kaushik

    2016-07-01

    Nematic elastomers and glasses are solids that display spontaneous distortion under external stimuli. Recent advances in the synthesis of sheets with controlled heterogeneities have enabled their actuation into nontrivial shapes with unprecedented energy density. Thus, these have emerged as powerful candidates for soft actuators. To further this potential, we introduce the key metric constraint which governs shape-changing actuation in these sheets. We then highlight the richness of shapes amenable to this constraint through two broad classes of examples which we term nonisometric origami and lifted surfaces. Finally, we comment on the derivation of the metric constraint, which arises from energy minimization in the interplay of stretching, bending, and heterogeneity in these sheets.

  18. Microstructure Evolution and Mechanical Properties of Al/Al-Mg/Al composite sheet metals

    NASA Astrophysics Data System (ADS)

    Cho, Jaehyung; Kim, Su-Hyeon; Kim, Hyoung-Wook; Lim, Cha-Yong; Kim, Eun-Young; Choi, Shi-Hoon

    2011-08-01

    Two different types of aluminum alloys of AA1050 and AA5182 were used to manufacture Al/Al-Mg/Al composite sheet metals by roll bonding technology at room temperature. The composite sheet metals were annealed at 400 °C and carried out uniaxial tension tests to investigate mechanical properties. Macroscopic mechanical properties are strongly dependent on the volume (or thickness) fraction of two component layers. Microstructure and texture evolution were also investigated during roll bonding process. The AA1050 sheets located in the outer layer mainly consist of shear texture components and the AA5182 sheet located in the center layer consists of plane strain texture components. With differential speeds of the top and bottom rolls, roll bonding was also carried out. Elongation along the RD and TD was improved at a speed difference of approximately 10%-20%.

  19. 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. PMID:26229979

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

    PubMed Central

    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. PMID:26229979

  1. 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.

  2. 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.

  3. Investigation of the static and dynamic fragmentation of metallic liquid sheets induced by random surface fluctuations

    NASA Astrophysics Data System (ADS)

    Durand, O.; Soulard, L.; Bourasseau, E.; Filippini, G.

    2016-07-01

    We perform molecular dynamics simulations to investigate the static and dynamic fragmentation of metallic liquid sheets of tin induced by random surface fluctuations. The static regime is analyzed by simulating sheets of different thicknesses, and the dynamic fragmentation is ensured by applying along the longitudinal direction of a sheet an instantaneous expansion velocity per initial unit length (expansion rate) with values ranging from 1 × 109 to 3 × 1010 s-1. The simulations show that the static/dynamic fragmentation becomes possible when the fluctuations of the upper and lower surfaces of the sheets can either overlap or make the local volume density of the system go down below a critical value. These two mechanisms cause locally in the sheet the random nucleation of pores of void, on a timescale that exponentially increases with the sheet thickness. Afterwards, the pores develop following distinct stages of growth, coalescence, and percolation, and later in time aggregates of liquid metal are formed. The simulations also show that the fragmentation of static sheets is characterized by relatively mono-dispersed surface and volume distributions of the pores and aggregates, respectively, whereas in extreme conditions of dynamic fragmentation (expansion rate typically in the range of 1 × 1010 s-1), the distributions are rather poly-dispersed and obey a power law decay with surface (volume). A model derived from the simulations suggests that both dynamic and static regimes of fragmentation are similar for expansion rates below typically 1 × 107 s-1.

  4. Adsorption of alkali and alkaline-earth metal atoms on the reconstructed graphene-like BN single sheet

    NASA Astrophysics Data System (ADS)

    Hao, Jun-Hua; Wang, Zheng-Jia; Wang, Yu-Fang; Yin, Yu-Hua; Jiang, Run; Jin, Qing-Hua

    2015-12-01

    A graphene-like BN single sheet with absorbed alkali and alkaline-earth metal atoms have been investigated by using a first-principles method within the framework of density functional theory (DFT). The electronic structure of BN sheet with adsorbed metal atoms is mainly determined by the metal electronic state which is near to the Fermi level owing to the wide band gap of pure BN sheet. So, we calculated the adsorption energy, charge transfer and work function after the metal adsorbed on BN sheet. We found that the interaction between the metal atoms and BN surface was very strong, and the stable adsorption site for all the adsorbed atoms concluded was high-coordination surface site (H-center) rather than the surface dangling bond sites from the perspective of simple bond-counting arguments. Our results indicate that the interaction of BN sheet with metal atoms could help in the development of metallic nanoscale devices.

  5. 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.

  6. Precise assembly of complex beta sheet topologies from de novo designed building blocks

    PubMed Central

    King, Indigo Chris; Gleixner, James; Doyle, Lindsey; Kuzin, Alexandre; Hunt, John F; Xiao, Rong; Montelione, Gaetano T; Stoddard, Barry L; DiMaio, Frank; Baker, David

    2015-01-01

    Design of complex alpha-beta protein topologies poses a challenge because of the large number of alternative packing arrangements. A similar challenge presumably limited the emergence of large and complex protein topologies in evolution. Here, we demonstrate that protein topologies with six and seven-stranded beta sheets can be designed by insertion of one de novo designed beta sheet containing protein into another such that the two beta sheets are merged to form a single extended sheet, followed by amino acid sequence optimization at the newly formed strand-strand, strand-helix, and helix-helix interfaces. Crystal structures of two such designs closely match the computational design models. Searches for similar structures in the SCOP protein domain database yield only weak matches with different beta sheet connectivities. A similar beta sheet fusion mechanism may have contributed to the emergence of complex beta sheets during natural protein evolution. DOI: http://dx.doi.org/10.7554/eLife.11012.001 PMID:26650357

  7. A metal sheet stiffened by a partially debonded composite quarter-plate. [stress analysis

    NASA Technical Reports Server (NTRS)

    Arin, K.

    1976-01-01

    An isotropic sheet stiffened by means of an orthotropic quarter-plate is considered. The quarter-plate is assumed to be perfectly bonded to the metal sheet everywhere except an area of debonding which may develop due to high stress concentrations. The adhesive which has a small constant thickness is treated as a shear spring. The loads are applied at infinity and supposed to be transmitted through the metal plate. Shear stress distribution between the two plates was obtained from the continuity of displacements along an area where they were bonded to each other.

  8. Detection of defects in formed sheet metal using medial axis transformation

    NASA Astrophysics Data System (ADS)

    Murmu, Naresh C.; Velgan, Roman

    2003-05-01

    In the metal forming processes, the sheet metals are often prone to various defects such as thinning, dents, wrinkles etc. In the present manufacturing environments with ever increasing demand of higher quality, detecting the defects of formed sheet metal using an effective and objective inspection system is the foremost norm to remain competitive in market. The defect detection using optical techniques aspire to satisfy its needs to be non-contact and fast. However, the main difficulties to achieve this goal remain essentially on the development of efficient evaluation technique and accurate interpretation of extracted data. The defect like thinning is detected by evaluating the deviations of the thickness in the formed sheet metal against its nominal value. The present evaluation procedure for determination of thickness applied on the measurements data is not without deficiency. To improve this procedure, a new evaluation approach based on medial axis transformation is proposed here. The formed sheet metals are digitized using fringe projection systems in different orientations, and afterwards registered into one coordinate frame. The medial axis transformation (MAT) is applied on the point clouds, generating the point clouds of MAT. This data is further processed and medial surface is determined. The thinning defect is detected by evaluating local wall thickness and other defects like wrinkles are determined using the shape recognition on the medial surface. The applied algorithm is simple, fast and robust.

  9. Flexible solution of the fixturing problem in sheet metal laser butt welding

    NASA Astrophysics Data System (ADS)

    Olsen, Flemming O.

    1994-09-01

    In 20 years laser welding of sheet metal has been demonstrated as a possible high-tech metal joining process. However, the major obstacle to the introduction of laser welding in for example car body manufacturing has been and is the fixturing problem. In case of laser butt welding of 0.5 - 1 mm thick steel sheets, the maximum acceptable gab between the sheets to be welded is in the range of 40 - 50 micrometer. Out of this demand two major problems arise: (1) the high precision required in weld preparation in terms of precise shape of the two sheets to be welded. (2) the problem of maintaining a narrow gab under welding, where thermal distortions, even though they are relatively small in this process, still will open the gap as the welding beam proceeds along the seam. In this paper a unique technique to overcome these problems will be described. The results of the experimental work described in this paper demonstrates the technique in 2D welding, where high quality butt welds has been demonstrated with virtually no clamping forces applied by utilizing a special seam preparation technique. Possibilities in car body manufacturing and other 3D sheet metal assembly by means of the flexible laser welding technique will be discussed.

  10. 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.

  11. 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.

  12. High-valent corrole metal complexes.

    PubMed

    Gross, Z

    2001-09-01

    This commentary concentrates on corrole complexes with the three metal ions that are most relevant to oxidation catalysis: chromium, manganese, and iron. Particular emphasis is devoted to the only recently introduced meso-triarylcorroles and a comparison with the traditionally investigated beta-pyrrole-substituted corroles. Based on a combination of spectroscopic methods, electrochemistry, and X-ray crystallography, it is concluded that in most high-valent metallocorroles the corrole is not oxidized. Both experimental (for (oxo)chromium(V) corrole) and computational (for (oxo)manganese(V) corrole) evidence indicate that the stabilization of high-valent metal ions by corroles originates from a combination of short metal-nitrogen bonds and large metal out-of-plane displacements in the corrole, which lead to quite unexpected interactions of the oxo-metal pi* orbitals with the in-plane orbitals of the corrole.

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

    PubMed

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

    2016-09-02

    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.

  14. 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.

  15. 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,…

  16. 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...

  17. AN INVESTIGATION OF SHEET METAL DEFORMATION BEHAVIOR DURING ELECTRO-HYDRAULIC FORMING (EHF)

    SciTech Connect

    Rohatgi, Aashish; Stephens, Elizabeth V.; Davies, Richard W.; Smith, Mark T.

    2013-06-10

    This presentation will describe the recent advances in our understanding of sheet metal behavior during electro-hydraulic forming (EHF) process. This presentation will describe results of selected experiments that were designed to explore various aspects of the EHF process and how flaws, invariably present in all materials, behave under high-rate forming conditions.

  18. Rubber-induced uniform laser shock wave pressure for thin metal sheets microforming

    NASA Astrophysics Data System (ADS)

    Shen, Zongbao; Wang, Xiao; Liu, Huixia; Wang, Yayuan; Wang, Cuntang

    2015-02-01

    Laser shock microforming of thin metal sheets is a new high velocity forming technique, which employs laser shock wave to deform the thin metal sheets. The spatial distribution of forming pressure is mainly dependent on the laser beam. A new type of laser shock loading method is introduced which gives a uniform pressure distribution. A low density rubber is inserted between the laser beam and the thin metal sheets. The mechanism of rubber-induced smoothing effect on confined laser shock wave is proposed. Plasticine is used to perform the smoothing effect experiments due to its excellent material flow ability. The influence of rubber on the uniformity of laser shock wave pressure is studied by measuring the surface micro topography of the deformed plasticine. And the four holes forming experiment is used to verify the rubber-induced uniform pressure on thin metal sheets surface. The research results show the possibility of smoothing laser shock wave pressure using rubber. And the good surface quality can be obtained under rubber dynamic loading.

  19. National Apprenticeship and Training Standards for the Sheet Metal Industry. Revised.

    ERIC Educational Resources Information Center

    Employment and Training Administration (DOL), Washington, DC. Bureau of Apprenticeship and Training.

    These national standards are designed to aid contractors, labor, and joint committees in setting up, conducting, and improving apprenticeship programs for individuals seeking to become skilled in the sheet metal industry. Covered in the individual sections are the following topics: the provisions of the apprenticeship standards (definitions,…

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. Pre-combustion CO2 capture by transition metal ions embedded in phthalocyanine sheets

    NASA Astrophysics Data System (ADS)

    Lü, Kun; Zhou, Jian; Zhou, Le; Chen, X. S.; Chan, Siew Hwa; Sun, Qiang

    2012-06-01

    Transition metal (TM) embedded two-dimensional phthalocyanine (Pc) sheets have been recently synthesized in experiments [M. Abel, S. Clair, O. Ourdjini, M. Mossoyan, and L. Porte, J. Am. Chem. Soc. 133, 1203 (2010)], 10.1021/ja108628r, where the transition metal ions are uniformly distributed in porous structures, providing the possibility of capturing gas molecules. Using first principles and grand canonical Monte Carlo simulations, TMPc sheets (TM = Sc, Ti, and Fe) are studied for pre-combustion CO2 capture by considering the adsorptions of H2/CO2 gas mixtures. It is found that ScPc sheet shows a good selectivity for CO2, and the excess uptake capacity of single-component CO2 on ScPc sheet at 298 K and 50 bar is found to be 2949 mg/g, larger than that of any other reported porous materials. Furthermore, electrostatic potential and natural bond orbital analyses are performed to reveal the underlying interaction mechanisms, showing that electrostatic interactions as well as the donation and back donation of electrons between the transition metal ions and the CO2 molecules play a key role in the capture.

  5. Development of measurement method of work hardeningbehavior in large plastic strain for sheet metal forging

    NASA Astrophysics Data System (ADS)

    Yoshikawa, Nobuo; Yamashita, Tomohiro; Shirakami, Satoshi; kada, Osamu; Yoshida, Tohru; Hiwatashi, Shunji

    2016-08-01

    For the purpose of accuracy improvement of sheet metal forging FE analysis, we have developed a new measurement method of work hardening behavior in large plastic strain by repeatedly performing simple shear test using pre-strained steel sheet. In this method, it is possible to measure work hardening behavior more than equivalent plastic strain 2.0. In addition, it was carried out a comparison between developed method and compression test in order to verify the validity of the results by the developed method. As a result, both results were in good agreement. The validity of developed method has been verified.

  6. 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.

  7. Optimum Design Of Addendum Surfaces In Sheet Metal Forming Process

    NASA Astrophysics Data System (ADS)

    Debray, K.; Sun, Z. C.; Radjai, R.; Guo, Y. Q.; Dai, L.; Gu, Y. X.

    2004-06-01

    The design of addendum surfaces in sheet forming process is very important for the product quality, but it is very time-consuming and needs tedious trial-error corrections. In this paper, we propose a methodology to automatically generate the addendum surfaces and then to optimize them using a forming modelling solver. The surfaces' parameters are taken as design variables and modified in course of optimization. The finite element mesh is created on the initial addendum surfaces and mapped onto the modified surfaces without remeshing operation. The Feasible Sequential Quadratic Programming (FSQP) is adopted as our algorithm of optimization. Two objective functions are used: the first one is the thickness function to minimize the thickness variation on the workpiece ; the second one is the appearance function aiming to avoid the scratching defects on the external surfaces of panels. The FSQP is combined with our "Inverse Approach" or "One Step Approach" which is a very fast forming solver. This leads to a very efficient optimization procedure. The present methodology is applied to a square box. The addendum surfaces are characterised by four geometrical variables. The influence of optimization criteria is studied and discussed.

  8. 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.

  9. 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

  10. 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.

  11. Integrated Modelling of Damage and Fracture in Sheet Metal Forming

    NASA Astrophysics Data System (ADS)

    Peerlings, R. H. J.; Mediavilla, J.; Geers, M. G. D.

    2007-05-01

    A framework for finite element simulations of ductile damage development and ductile fracture during metal forming is presented. The damage evolution is described by a phenomenological continuum damage model. Crack growth and fracture are treated as the ultimate consequences of the damage process. Computationally, the initiation and growth of cracks is traced by an adaptive remeshing strategy, thereby allowing for opening crack faces. The application of the method to the fabrication of food-can lids demonstrates its capabilities, but also some of its limitations.

  12. Effect of Forming Speed on Plastic Bending of Adhesively Bonded Sheet Metals

    NASA Astrophysics Data System (ADS)

    Takiguchi, Michihiro; Yoshida, Fusahito

    Using highly ductile acrylic adhesive, the present authors proposed a new technique of plastic bending of adhesively bonded sheet metals. In this process, the suppression of large transverse shear deformation occurring in the adhesive layer, which in some cases would induce the geometrical imperfection (so-called ‘gull-wing bend') and the delamination of the sheet, is one of the most important technical issues. In the present work, the effect of forming speed on bending deformation was investigated. From experimental observations in V-bending experiments of adhesively bonded aluminium sheets, as well as the corresponding numerical simulations which consider the viscoplasticity nature of the adhesive resin, it was found that the large shear deformation and ‘gull-wing bend' are successfully suppressed by high-speed forming since the deformation resistance of the adhesive resin becomes higher at a high strain rate.

  13. Wide-band-gap wrinkled nanoribbon-like structures in a continuous metallic graphene sheet

    NASA Astrophysics Data System (ADS)

    Li, Si-Yu; Zhou, Mei; Qiao, Jia-Bin; Duan, Wenhui; He, Lin

    2016-08-01

    To generate a moderate band gap in a graphene monolayer is a very important but rather difficult task. A rare working solution of this problem is to cut it into one-dimensional (1D) nanometer-wide ribbons. Here we show that, instead of cutting the graphene monolayer, a wide band gap can be created in a unique 1D strained structure, i.e., a wrinkled graphene-nanoribbon-like (GNR-like) structure, of a continuous graphene sheet via strong hybridization between the graphene and the metal substrate. The wrinkled GNR-like structures with widths of only a few nanometers are observed in a continuous graphene sheet grown on a Rh foil by using thermal strain engineering. Spatially resolved scanning tunneling spectroscopy revealed a band-gap opening of a few hundred meV in the GNR-like structure in an otherwise continuous metallic graphene sheet, directly demonstrating the realization of a metallic-semiconducting-metallic junction entirely in a graphene monolayer.

  14. 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

  15. Fine micro-welding of thin metal sheet by high speed laser scanning

    NASA Astrophysics Data System (ADS)

    Okamoto, Yasuhiro; Gillner, Arnold; Olowinsky, Alexander; Gedicke, Jens; Uno, Yoshiyuki

    2007-05-01

    Recently, since the size of component becomes smaller, then the welding of thin metal sheet has been required. Besides, the flexibility of process is important according to the accessibility especially for small components. Fraunhofer Institute for Laser Technology had developed the SHADOW ® welding technology, in which the high speed joining with small distortion is possible using pulsed Nd:YAG laser. The possibility of high speed and high quality welding had been reported by using single-mode fiber laser. The combination of micro beam and high speed laser scanning has the advantages for thin metal sheet welding. Therefore, the characteristics of micro-welding for thin metal sheet were investigated by high speed laser scanning, in which the welding was carried out by high speed scanner system with single-mode fiber laser and pulsed Nd:YAG laser. The proper welding region was narrow by the laser beam with a large focus diameter of 160 μm without pulse control, while a small focus diameter of 22 μm can control the welding state widely. A small focus diameter can perform the excellent welding seam from the extreme beginning without pulse control. The penetration depth can be controlled by the energy density with a small focus diameter of 22 μm at the energy densities less than 1 J/mm2. Besides, the unique periodic structure appeared at the high velocity of beam scanning with a small focus diameter. Moreover, the overlap welding of 25 μm thickness sheet can be performed regardless of small gap distance between two sheets by the laser beam with a small focus diameter of 22 μm.

  16. Electric-Field-Assisted Directed Assembly of Transition Metal Dichalcogenide Monolayer Sheets.

    PubMed

    Deng, Donna D; Lin, Zhong; Elías, Ana Laura; Perea-Lopez, Nestor; Li, Jie; Zhou, Chanjing; Zhang, Kehao; Feng, Simin; Terrones, Humberto; Mayer, Jeffrey S; Robinson, Joshua A; Terrones, Mauricio; Mayer, Theresa S

    2016-05-24

    Directed assembly of two-dimensional (2D) layered materials, such as transition metal dichalcogenides, holds great promise for large-scale electronic and optoelectronic applications. Here, we demonstrate controlled placement of solution-suspended monolayer tungsten disulfide (WS2) sheets on a substrate using electric-field-assisted assembly. Micrometer-sized triangular WS2 monolayers are selectively positioned on a lithographically defined interdigitated guiding electrode structure using the dielectrophoretic force induced on the sheets in a nonuniform field. Triangular sheets with sizes comparable to the interelectrode gap assemble with an observed preferential orientation where one side of the triangle spans across the electrode gap. This orientation of the sheets relative to the guiding electrode is confirmed to be the lowest energy configuration using semianalytical calculations. Nearly all sheets assemble without observable physical deformation, and postassembly photoluminescence and Raman spectroscopy characterization of the monolayers reveal that they retain their as-grown crystalline quality. These results show that the field-assisted assembly process may be used for large-area bottom-up integration of 2D monolayer materials for nanodevice applications. PMID:27082162

  17. 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.

  18. 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).

  19. 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.

  20. Advanced material testing in support of accurate sheet metal forming simulations

    NASA Astrophysics Data System (ADS)

    Kuwabara, Toshihiko

    2013-05-01

    This presentation is a review of experimental methods for accurately measuring and modeling the anisotropic plastic deformation behavior of metal sheets under a variety of loading paths: biaxial compression test, hydraulic bulge test, biaxial tension test using a cruciform specimen, multiaxial tube expansion test using a closed-loop electrohydraulic testing machine for the measurement of forming limit strains and stresses, combined tension-shear test, and in-plane stress reversal test. Observed material responses are compared with predictions using phenomenological plasticity models to highlight the importance of accurate material testing. Special attention is paid to the plastic deformation behavior of sheet metals commonly used in industry, and to verifying the validity of constitutive models based on anisotropic yield functions at a large plastic strain range. The effects of using appropriate material models on the improvement of predictive accuracy for forming defects, such as springback and fracture, are also presented.

  1. Prediction Of Formability In Sheet Metal Forming Processes Using A Local Damage Model

    SciTech Connect

    Teixeira, P.; Santos, Abel; Cesar Sa, J.; Andrade Pires, F.; Barata da Rocha, A.

    2007-05-17

    The formability in sheet metal forming processes is mainly conditioned by ductile fracture resulting from geometric instabilities due to necking and strain localization. The macroscopic collapse associated with ductile failure is a result of internal degradation described throughout metallographic observations by the nucleation, growth and coalescence of voids and micro-cracks. Damage influences and is influenced by plastic deformation and therefore these two dissipative phenomena should be coupled at the constitutive level. In this contribution, Lemaitre's ductile damage model is coupled with Hill's orthotropic plasticity criterion. The coupling between damaging and material behavior is accounted for within the framework of Continuum Damage Mechanics (CDM). The resulting constitutive equations are implemented in the Abaqus/Explicit code, for the prediction of fracture onset in sheet metal forming processes. The damage evolution law takes into account the important effect of micro-crack closure, which dramatically decreases the rate of damage growth under compressive paths.

  2. Numerical simulation on multi-gripper stretch forming process for sheet metal

    NASA Astrophysics Data System (ADS)

    Wang, Y.; Li, M. Z.; Peng, H. L.; Gu, S. H.

    2013-05-01

    Multi-gripper stretch forming (MGSF) is a new flexible forming process compared to traditional stretching forming process. Two kinds of MGSF process, back-vertical drawing (BVD) and front-vertical drawing (FVD) are compared in this study. Spherical-curved part is selected as the research object, and the finite numerical modes for BVD and FVD have been established, and the simulation results are carried out by dynamic explicit finite element analysis. The numerical results indicated that the sheet metal can get the shape of the die at a lower strain ratio and the stretch strain distribution was more uniform by the FVD, which can improve the forming quality of the formed parts. In addition, the sheet metal can be formed by FVD under smaller hydraulic cylinder strokes. The results may provide useful guidance on optimizing the MGSF equipment structure.

  3. The concept of virtual material testing and its application to sheet metal forming simulations

    NASA Astrophysics Data System (ADS)

    Butz, A.; Pagenkopf, J.; Baiker, M.; Helm, D.

    2016-08-01

    A crystal plasticity based full-field microstructure simulation approach is used to virtually determine mechanical properties of sheet metals. Microstructural features like the specific grain morphology and the crystallographic texture are taken into account to predict the plastic anisotropy. A special focus is on the determination of the Lankford coefficients and on the yield surface under plane stress conditions. Compared to experimental procedures, virtual material testing allows to generate significantly more data points on the yield surface. This data is used to calibrate anisotropic elasto-plastic material models which are commonly used for sheet metal forming simulations. A numerical study is carried out to analyze the influence of the chosen points on the yield surface on the calibration procedure.

  4. 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.

  5. Non-Local Ductile Damage Formulations for Sheet Bulk Metal Forming

    NASA Astrophysics Data System (ADS)

    Beese, Steffen; Loehnert, Stefan; Wriggers, Peter

    2016-08-01

    A ductile damage model for sheet bulk metal forming processes and its efficient and accurate treatment in the context of the Finite Element Method is presented. The damage is introduced as a non-local field to overcome pathological mesh dependency. Since standard elements tend to show volumetric locking in the bulk forming process a mixed formulation is implemented in the commercial software simufact.forming to obtain better results.

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

    NASA Astrophysics Data System (ADS)

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

    2007-05-01

    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.

  8. An expert system for ensuring the reliability of the technological process of cold sheet metal forming

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

    In order to exclude periodic defects in the parts manufacturing obtained by cold sheet metal forming a method of automated estimation of technological process reliability was developed. The technique is based on the analysis of reliability factors: detail construction, material, mechanical and physical requirements; hardware settings, tool characteristics, etc. In the work the expert system is presented based on a statistical accumulation of the knowledge of the operator (technologist) and decisions of control algorithms.

  9. 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. PMID:27127499

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

    PubMed Central

    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. PMID:27127499

  11. 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...

  12. 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...

  13. 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...

  14. 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...

  15. 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...

  16. 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...

  17. 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...

  18. 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...

  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. 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...

  1. Methyl Complexes of the Transition Metals.

    PubMed

    Campos, Jesús; López-Serrano, Joaquín; Peloso, Riccardo; Carmona, Ernesto

    2016-05-01

    Organometallic chemistry can be considered as a wide area of knowledge that combines concepts of classic organic chemistry, that is, based essentially on carbon, with molecular inorganic chemistry, especially with coordination compounds. Transition-metal methyl complexes probably represent the simplest and most fundamental way to view how these two major areas of chemistry combine and merge into novel species with intriguing features in terms of reactivity, structure, and bonding. Citing more than 500 bibliographic references, this review aims to offer a concise view of recent advances in the field of transition-metal complexes containing M-CH3 fragments. Taking into account the impressive amount of data that are continuously provided by organometallic chemists in this area, this review is mainly focused on results of the last five years. After a panoramic overview on M-CH3 compounds of Groups 3 to 11, which includes the most recent landmark findings in this area, two further sections are dedicated to methyl-bridged complexes and reactivity.

  2. 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.

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

    SciTech Connect

    Gerlach, Joerg; Kessler, Lutz; Paul, Udo; Roesen, Hartwig

    2007-05-17

    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.

  4. 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.

  5. Formulation of Contact Problems in Sheet Metal Forming Simulation Using Local Interpolation for Tool Surfaces

    NASA Astrophysics Data System (ADS)

    Hama, Takayuki; Takamura, Masato; Makinouchi, Akitake; Teodosiu, Cristian; Takuda, Hirohiko

    The treatment of contact between a sheet and tools is one of the most difficult problems to deal with in finite-element simulations of the sheet metal forming processes. In order to obtain more accurate tool models without increasing the number of elements, this paper describes new techniques for the contact problem using a local interpolation for tool surfaces proposed by Nagata. The Nagata patch enables the creation of tool models that are much more accurate in shape than those of the conventional polyhedral representations. Contact search algorithms between the sheet nodes and the interpolated tool surfaces and a consistent contact tangent stiffness matrix for the sliding sheet nodes were formulated. The proposed contact search algorithms allow robust and accurate contact analyses. The developed algorithms were introduced into the static-explicit elastoplastic finite-element method code STAMP3D. Simulations of a square-cup deep-drawing process with a very coarsely discretized punch model were carried out. The simulated results showed that the proposed algorithms yield the proper deformation process, thus demonstrating the validity of the proposed techniques.

  6. Application of sintered titanium alloys to metal denture bases: a study of titanium powder sheets for complete denture base.

    PubMed

    Doi, H; Harrori, M; Hasegawa, K; Yoshinari, M; Kawada, E; Oda, Y

    2001-02-01

    The purpose of this study was the fabrication of titanium powder sheets to enable the application of sintered titanium alloys as metal denture bases. The effects of titanium particle shape and size, binder content, and plasticizer content on the surface smoothness, tensile strength and elongation of titanium powder sheets was investigated. To select a suitable ratio of powdered metal contents for application as a metal denture base, the effects of aluminum content in Ti sheets and various other powder metal contents in Ti-Al sheets on the density, sintering shrinkage, and bending strength were evaluated. Based on the results of the above experiments, we developed a mixed powder sheet composed of 83Ti-7Al-10Cr with TA45 titanium powder (atomized, -45 microm), and 8 mass% binder content. This titanium alloy sheet had good formability and ductility. Its sintered titanium alloy had a density of 3.2 g/cm3, sintering shrinkage of 3.8%, and bending strength of 403 MPa. The titanium alloy sheet is clinically acceptable for fabricating denture bases. PMID:11484793

  7. Application of sintered titanium alloys to metal denture bases: a study of titanium powder sheets for complete denture base.

    PubMed

    Doi, H; Harrori, M; Hasegawa, K; Yoshinari, M; Kawada, E; Oda, Y

    2001-02-01

    The purpose of this study was the fabrication of titanium powder sheets to enable the application of sintered titanium alloys as metal denture bases. The effects of titanium particle shape and size, binder content, and plasticizer content on the surface smoothness, tensile strength and elongation of titanium powder sheets was investigated. To select a suitable ratio of powdered metal contents for application as a metal denture base, the effects of aluminum content in Ti sheets and various other powder metal contents in Ti-Al sheets on the density, sintering shrinkage, and bending strength were evaluated. Based on the results of the above experiments, we developed a mixed powder sheet composed of 83Ti-7Al-10Cr with TA45 titanium powder (atomized, -45 microm), and 8 mass% binder content. This titanium alloy sheet had good formability and ductility. Its sintered titanium alloy had a density of 3.2 g/cm3, sintering shrinkage of 3.8%, and bending strength of 403 MPa. The titanium alloy sheet is clinically acceptable for fabricating denture bases.

  8. 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.

  9. 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.

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

    PubMed

    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

  11. 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

  12. 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

  13. Metal complex polymers for electroluminescent applications

    SciTech Connect

    Tao, X.T.; Suzuki, H.; Zhang, Y.D.; Watanabe, T.; Miyata, S.; Wada, T.; Sasabe, H.

    1998-07-01

    The authors report the synthesis and characterization of a soluble metal complex polymer for electroluminescent (EL) applications. The polymer was prepared by the reaction of a zinc Schiff base with 4,4{prime}-diphenylmethane-diisocyanate. The polymer is amorphous and with glass transition temperature of 156 C and is soluble in common organic solvents such as chloroform, tetrahydrofuran (THF), and N-methylpyrrolidinone (NMP). The zinc Schiff base, and the polyurethane (PU) shows strong photoluminescence under a UV-lamp illumination. Single and double layer EL devices consisting ITO/hole transfer layer (HTL)/PU/AL have been fabricated and characterized. The results indicated that the complex polymer could act as both electron transport and emissive layers for EL devices.

  14. Flat sheet metal girders with very thin metal web. Part III : sheet metal girders with spars resistant to bending - the stress in uprights - diagonal tension fields

    NASA Technical Reports Server (NTRS)

    Wagner, Herbert

    1931-01-01

    This report continues the work presented in NACA-TM 605 and expands the scope to include the change in specific number of wrinkles from direction x to z, so that b and f become variable in direction z. Moreover, it seems likely that b and f increase from the edge toward the center if the sheet is infinitely thin.

  15. Simulation of ultra-thin sheet metal forming using phenomenological and crystal plasticity models

    NASA Astrophysics Data System (ADS)

    Adzima, F.; Manach, PY; Balan, T.; Tabourot, L.; Toutain, S.; Diot, JL

    2016-08-01

    Micro-forming of ultra-thin sheet metals raises numerous challenges. In this investigation, the predictions of state-of-the-art crystal plasticity (CP) and phenomenological models are compared in the framework of industrial bending-dominated forming processes. Sheet copper alloys 0.1mm-thick are considered, with more than 20 grains through the thickness. Consequently, both model approaches are valid on theoretical ground. The phenomenological models’ performance was conditioned by the experimental database used for parameter identification. The CP approach was more robust with respect to parameter identification, while allowing for a less flexible description of kinematic hardening, at the cost of finer mesh and specific grain-meshing strategies. The conditions for accurate springback predictions with CP-based models are investigated, in an attempt to bring these models at the robustness level required for industrial application.

  16. 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.

  17. 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

  18. 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.

  19. Development of Dynamic Explicit Crystallographic Homogenization Finite Element Analysis Code to Assess Sheet Metal Formability

    NASA Astrophysics Data System (ADS)

    Nakamura, Yasunori; Tam, Nguyen Ngoc; Ohata, Tomiso; Morita, Kiminori; Nakamachi, Eiji

    2004-06-01

    The crystallographic texture evolution induced by plastic deformation in the sheet metal forming process has a great influence on its formability. In the present study, a dynamic explicit finite element (FE) analysis code is newly developed by introducing a crystallographic homogenization method to estimate the polycrystalline sheet metal formability, such as the extreme thinning and "earing." This code can predict the plastic deformation induced texture evolution at the micro scale and the plastic anisotropy at the macro scale, simultaneously. This multi-scale analysis can couple the microscopic crystal plasticity inhomogeneous deformation with the macroscopic continuum deformation. In this homogenization process, the stress at the macro scale is defined by the volume average of those of the corresponding microscopic crystal aggregations in satisfying the equation of motion and compatibility condition in the micro scale "unit cell," where the periodicity of deformation is satisfied. This homogenization algorithm is implemented in the conventional dynamic explicit finite element code by employing the updated Lagrangian formulation and the rate type elastic/viscoplastic constitutive equation. At first, it has been confirmed through a texture evolution analyses in cases of typical deformation modes that Taylor's "constant strain homogenization algorithm" yields extreme concentration toward the preferred crystal orientations compared with our homogenization one. Second, we study the plastic anisotropy effects on "earing" in the hemispherical cup deep drawing process of pure ferrite phase sheet metal. By the comparison of analytical results with those of Taylor's assumption, conclusions are drawn that the present newly developed dynamic explicit crystallographic homogenization FEM shows more reasonable prediction of plastic deformation induced texture evolution and plastic anisotropy at the macro scale.

  20. 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...

  1. 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...

  2. 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...

  3. 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...

  4. 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...

  5. Macroscopic and Strong Ribbons of Functionality-Rich Metal Oxides from Highly Ordered Assembly of Unilamellar Sheets.

    PubMed

    Hou, Junyu; Zheng, Yuanchuan; Su, Yanli; Zhang, Weikun; Hoshide, Tatsumasa; Xia, Feifei; Jie, Jiansheng; Li, Qingwen; Zhao, Zhigang; Ma, Renzhi; Sasaki, Takayoshi; Geng, Fengxia

    2015-10-14

    The strong interest in macroscopic graphene and/or carbon nanotube (CNT) fiber has highlighted that anisotropic nanostructured materials are ideal components for fabricating fiber assemblies. Prospectively, employing two-dimensional (2D) crystals or nanosheets of functionality-rich transition metal oxides would notably enrich the general knowledge for desirable fiber constructions and more importantly would greatly broaden the scope of functionalities. However, the fibers obtained up to now have been limited to carbon-related materials, while those made of 2D crystals of metal oxides have not been achieved, probably due to the intrinsically low mechanical stiffness of a molecular sheet of metal oxides, which is only few hundredths of that for graphene. Here, using 2D titania sheets as an illustrating example, we present the first successful fabrication of macroscopic fiber of metal oxides composed of highly aligned stacking sheets with enhanced sheet-to-sheet binding interactions. Regardless of the intrinsically weak Ti-O bond in molecular titania sheets, the optimal fiber manifested mechanical performance comparable to that documented for graphene or CNTs. This work provided important hints for devising optimized architecture in macroscopic assemblies, and the rich functionalities of titania promises fibers with limitless promise for a wealth of innovative applications.

  6. Interaction of a High-Power Laser Beam with Metal Sheets

    SciTech Connect

    Boley, C D; Cutter, K P; Fochs, S N; Pax, P H; Rotter, M D; Rubenchik, A M; Yamamoto, R M

    2009-06-24

    Experiments with a high-power laser beam directed onto thin aluminum sheets, with a large spot size, demonstrate that airflow produces a strong enhancement of the interaction. The enhancement is explained in terms of aerodynamic effects. As laser heating softens the material, the airflow-induced pressure difference between front and rear faces causes the metal to bulge into the beam. The resulting shear stresses rupture the material and remove it at temperatures well below the melting point. The material heating is shown to conform to an elementary model. We present an analytic model of elastic bulging. Scaling with respect to spot size, wind speed, and material parameters is determined.

  7. European Bronze Age Sheet Metal Objects: 3,000 Years of High-Level Bronze Manufacture

    NASA Astrophysics Data System (ADS)

    Mödlinger, Marianne; El Morr, Ziad

    2014-01-01

    This article focuses on the manufacture and usage of selected sheet metal objects from helmets, a vessel, and two shields from the European Bronze Age and Early Iron Age, which date from the thirteenth to seventh centuries BC. Manufacturing traces on the surface, as well as metallographic investigations and the analyses of the alloy composition with scanning electron microscope-energy-dispersive x-ray spectroscopy, provided an insight into the manufacturing techniques and the production of valuable, high-status objects, and highlighted the potential changes in manufacturing techniques and alloys used during different time periods.

  8. Effects of Temperature and Forming Speed on Plastic Bending of Adhesively Bonded Sheet Metals

    NASA Astrophysics Data System (ADS)

    Takiguchi, Michihiro; Yoshida, Tetsuya; Yoshida, Fusahito

    This paper deals with the temperature and rate-dependent elasto-viscoplasticity behaviour of a highly ductile acrylic adhesive and its effect on plastic bending of adhesively bonded sheet metals. Tensile lap shear tests of aluminium single-lap joints were performed at various temperature of 10-40°C at several tensile speeds. Based on the experimental results, a new constitutive model of temperature and rate-dependent elasto-viscoplasticity of the adhesive is presented. From V-bending experiments and the corresponding numerical simulation, it was found that the gull-wing bend is suppressed by high-speed forming at a lower temperature.

  9. Influence of surface processing on the fracture strength of structurally integrated PZT fibers in shaped sheet metal parts

    NASA Astrophysics Data System (ADS)

    Schmidt, Marek; Wittstock, Volker; Müller, Michael

    2015-03-01

    In the present state of the art, the function integration into lightweight metal structures is generally based upon adhesive bonding of sensors or actuators to the surface. A new technology enables a direct structural integration of lead-zirconatetitanate (PZT) fibers into local microstructures of metal sheets and subsequent joining by forming. This provides a complete functional integration of the piezoelectric ceramic in the metal for sensors and actuators purposes. In a further process step, the composite is shaped by deep drawing with a cup with double curvature radii of 100 mm into a complex 3D surface. During the shaping process it is expected that the PZT- fibers get damaged with the result of degradation of the piezoelectric function. This paper describes the application of various surface processing methods to improve the shaping behavior of the piezoceramic fibers. The production of interconnected parallel fibers is based on piezoceramic plates. The plates are treated by different surface processing. One experimental series is lapped and another series is extra polished by chemical mechanical polishing (CMP). The resulting plates were examined with regard to the fracture strength and the degradation of the piezoelectric properties during manufacturing and operation. It has been shown that the lapped and polished plates have a clearly better persistence with regard to the shaping processes compared to the unprocessed plates. The best results in this process were achieved by the polished plates, which is also transferable to the fibers. Furthermore, the piezoelectric characteristics were better preserved by the lapped and polished plates and fibers.

  10. 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.

  11. 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…

  12. Thin Porous Metal Sheet-Supported NaA Zeolite Membrane for Water/Ethanol Separation

    SciTech Connect

    Zhang, Jian; Liu, Wei

    2011-04-01

    This paper reports preparation and separation testing results of water-selective zeolite membrane, such as NaA (or 4A-type), supported on a robust, porous metal sheet of 50um thickness. The thin sheet support is of large potential for development of a low-cost, inorganic membrane module of high surface area packing density. The porous Ni alloy sheet of micrometer or sub-micrometer mean pore size, which was prepared by a proprietary process, is used to evaluate different zeolite membrane deposition methods and conditions. The membranes are characterized by SEM, XRD and water/ethanol separation tests. Quality NaA zeolite membrane at thickness <2um is obtained with the secondary hydrothermal growth method. This membrane shows water/ethanol separation factor of >10,000 and water permeation flux of about 4 kg/(m2•h) at 75ºC with a feed of 10wt% water in ethanol. The membrane is also demonstrated with good stability in 66-hour continuous testing at 75ºC and 90ºC.

  13. 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%.

  14. First-principles study of electronic and magnetic properties of transition metal adsorbed h-BNC2 sheets.

    PubMed

    Srivastava, Pooja; Deshpande, Mrinalini; Sen, Prasenjit

    2011-12-28

    Adsorption of Fe, Co and Ni atoms on a hybrid hexagonal sheet of graphene and boron nitride is studied using density functional methods. Most favorable adsorption sites for these adatoms are identified for different widths of the graphene and boron nitride regions. Electronic structure and magnetic properties of the TM-adsorbed sheets are then studied in detail. The TM atoms change the electronic structure of the sheet significantly, and the resulting system can be a magnetic semiconductor, semi-metal, or a non-magnetic semiconductor depending on the TM chosen. This gives tunability of properties which can be useful in novel electronics applications. Finally, barriers for diffusion of the adatoms on the sheet are calculated, and their tendency to agglomerate on the sheet is estimated. PMID:22068843

  15. 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.

  16. 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

  17. The FE simulation research on roll bending process of complex sheet with padding assisted

    NASA Astrophysics Data System (ADS)

    Wei, Tianhai; Zhao, Yixi; Song, Bo; Chen, Baoguo; Yu, Zhongqi

    2013-05-01

    The roll bending process with padding assisted is a new profile forming method. In this paper, the aluminum sheet 2024-T3 with variable thickness is roll bended through three-roller with padding assisted. The finite element model is established with ABAQUS software, the forming process and springback are successfully simulated. The padding material and the padding thickness are discussed based on FE model. The result showed that the PA6-G, with a higher strength, is a preferred padding material. The good forming result will be obtained if the padding of thicker thickness is chosen among 6mm and 9mm. This research provides some useful references for the real forming process of complex sheet.

  18. An interpolation type anisotropic yield function and its application in sheet metal forming simulation

    NASA Astrophysics Data System (ADS)

    Xiao, R. Q.; Peng, F.; Dong, X. H.

    2016-08-01

    Affected by texture, Bauschinger effect and different deformation mechanisms, plastic deformation behavior of the sheet metals are complicated, especially for HCP metals, such as magnesium and titanium. With more and more enhanced demand to describe the materials’ yield behavior precisely and efficiently in numerical simulation, application of traditional continuous type yield functions encounters great challenge. So an interpolation type anisotropic yield function for plane stress is proposed. This yield function is represented by a yield surface in the polar coordinate system. The radius vector to the yield surface represents the yield stress at yielding, while the outer normal is related with the R values. The physical meaning of the parameters is directly defined. Accuracy, efficiency and flexibility can be achieved by application of such yield functions.

  19. 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.

  20. Characterization of the Bauschinger effect in sheet metal undergoing large strain reversals in bending

    NASA Astrophysics Data System (ADS)

    Hanzon, Drew Wyatt

    This work consists on the quantification of sheet metal uniaxial stress-strain reversals from pure bending tests. Bending strains to approximately 10% were measured by strain gages and interferometry. Bending-unbending moments and strains were modeled and compared closely to the experimental data. The reverse uniaxial stress-strains curves were determined from the optimal fit of the model. Bauschinger effects were described by the reverse uniaxial response at the elasto-plastic range, between the elastic and the large strain, power fit ranges. Arc and straight line fittings on the lnsigma-lnepsilon scale proved accurate to describe the elasto-plastic behavior. Reverse uniaxial data determined for DP590 and DP780 steels and two Aluminum alloys showed significant Bauschinger effects with distinct features. For the DP steels the magnitudes of the reverse compressive sigma-epsilon curves compared moderately higher, and merging to a power curve with parameters K, n previously defined by tension testing. Bauschinger effects at small reversed strains were less pronounced for the aluminum alloys. However, at higher strains the reverse elasto-plastic response softened considerably, and during the unbending span the magnitudes of the reverse compressive strains remained below the corresponding K, n tensile values. The results showed pure bending as an efficient, simple to use technique to generate sigma-epsilon data for sheet metal at large reverse strains without the complicating restraining hardware required by direct compression methods.

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

    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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. Weldability of thin sheet metals during small-scale resistance spot welding using an alternating-current power supply

    NASA Astrophysics Data System (ADS)

    Zhou, Y.; Gorman, P.; Tan, W.; Ely, K. J.

    2000-09-01

    The resistance weldability of 0.2-mm-thick sheet aluminum, brass, and copper in small-scale resistance spot welding (SSRSW) was studied. The effects of electrode materials and process parameters on joint strength and nugget size were investigated. The welding current ranges for SSRSW of the sheet metals were determined based on the minimum current that produced a required nugget diameter and maximum currents that did not result in electrode-sheet sticking or weld metal expulsion. A qualitative analysis indicated that resistance weldability of the metals is not only determined by their resistivity (or thermal conductivity) but is also affected by other physical properties (such as melting point, latent heat of fusion and specific heat).

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. 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.

  12. Design of stable β-sheet-based cyclic peptide assemblies assisted by metal coordination: selective homo- and heterodimer formation.

    PubMed

    Panciera, Michele; Amorín, Manuel; Castedo, Luis; Granja, Juan R

    2013-04-01

    Metal-directed supramolecular construction represents one of the most powerful tools to prepare a large variety of structures and functions. The ability of metals to organize different numbers and types of ligands with a variety of geometries (linear, trigonal, octahedral, etc.) expands the supramolecular synthetic architecture. We describe here the precise construction of homo- and heterodimeric cyclic peptide entities through coordination of a metal (Pd, Au) and to β-sheet-type hydrogen-bonding interactions. The selective coordination properties of the appropriate metal allow control over the cross-strand interaction between the two-peptide strands. PMID:23423964

  13. Non-Local Damage Modelling of Sheet Metal Forming Processes with ALE Formulation

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

    The modelling of material degradation due to nucleation, growth and coalescence of micro-voids is vital in sheet metal forming process due to the large deformation typically experienced by the part. Nonlocal damage modelling or nonlocal continuum is gaining a lot of interest because it is an effective approach to modelling the strain-softening, whilst avoiding the spurious localization that gives rise to strong mesh sensitivity in numerical computations. However to accurately resolve the evolving narrow bands of highly localised strain, it is necessary to use sufficient computational grids. In this paper an ALE formulation is used for modelling the localization pattern. An approach for relocating the node points is presented and explored.

  14. 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.

  15. Calculation of Forming Limits for Sheet Metal using an Enhanced Continuous Damage Fracture Model

    NASA Astrophysics Data System (ADS)

    Nguyen, Ngoc-Trung; Kim, Dae-Young; Kim, Heon Young

    2011-08-01

    An enhanced continuous damage fracture model was introduced in this paper to calculate forming limits of sheet metal. The fracture model is a combination of a fracture criterion and a continuum damage constitutive law. A modified McClintock void growth fracture criterion was incorporated with a coupled damage-plasticity Gurson-type constitutive law. Also, by introducing a Lode angle dependent parameter to define the loading asymmetry condition, the shear effect was phenomenologically taken into account. The proposed fracture model was implemented using user-subroutines in commercial finite element software. The model was calibrated and correlated by the uniaxial tension, shear and notched specimens tests. Application of the fracture model for the LDH tests was discussed and the simulation results were compared with the experimental data.

  16. Modeling and FE Simulation of Quenchable High Strength Steels Sheet Metal Hot Forming Process

    NASA Astrophysics Data System (ADS)

    Liu, Hongsheng; Bao, Jun; Xing, Zhongwen; Zhang, Dejin; Song, Baoyu; Lei, Chengxi

    2011-08-01

    High strength steel (HSS) sheet metal hot forming process is investigated by means of numerical simulations. With regard to a reliable numerical process design, the knowledge of the thermal and thermo-mechanical properties is essential. In this article, tensile tests are performed to examine the flow stress of the material HSS 22MnB5 at different strains, strain rates, and temperatures. Constitutive model based on phenomenological approach is developed to describe the thermo-mechanical properties of the material 22MnB5 by fitting the experimental data. A 2D coupled thermo-mechanical finite element (FE) model is developed to simulate the HSS sheet metal hot forming process for U-channel part. The ABAQUS/explicit model is used conduct the hot forming stage simulations, and ABAQUS/implicit model is used for accurately predicting the springback which happens at the end of hot forming stage. Material modeling and FE numerical simulations are carried out to investigate the effect of the processing parameters on the hot forming process. The processing parameters have significant influence on the microstructure of U-channel part. The springback after hot forming stage is the main factor impairing the shape precision of hot-formed part. The mechanism of springback is advanced and verified through numerical simulations and tensile loading-unloading tests. Creep strain is found in the tensile loading-unloading test under isothermal condition and has a distinct effect on springback. According to the numerical and experimental results, it can be concluded that springback is mainly caused by different cooling rats and the nonhomogengeous shrink of material during hot forming process, the creep strain is the main factor influencing the amount of the springback.

  17. High power laser beam melting of Ti6Al4V on formed sheet metal to achieve hybrid structures

    NASA Astrophysics Data System (ADS)

    Ahuja, Bhrigu; Schaub, Adam; Karg, Michael; Schmidt, Roman; Merklein, Marion; Schmidt, Michael

    2015-03-01

    Motivated by the desire to combine the advantages of two manufacturing concepts, namely Additive Manufacturing and sheet metal forming, the concept of hybrid processes emerged. Laser Beam Melting process with its characteristic layer by layer fabrication methodology has already been proved to be successful in fabricating fully dense 3D structures with micro sized Ti6Al4V powder. The presented research focuses on direct fabrication of Ti6 Al4V Additive Structures on a thin pre-formed Ti6 Al4V sheet metal substrate. In the state of the art Laser Beam Melting process, fabrication of solid structures is done on a support structure attached to a thick conventionally manufactured base plate. The state of the art process also uses a 200°C pre-heating of the fabrication platform in order to reduce the effect of heat induced stresses on the fabricated structures. Within the hybrid fabrication concept, 3D structures are directly fabricated on a thin sheet metal and the thermodynamic conditions are significantly different in comparison to the conventional process. The research aims at understanding the fundamental aspects of the interaction between the formed sheet metal and additive structure determines the corresponding mechanical characteristics. The interaction process during the fabrication exposes the alloy locally to non-optimum thermal cycles and the research therefore aims to understand the various influencing factors involved during the fabrication process. The system technology modifications required to achieve the aimed fabrication are also discussed in the presented research.

  18. Development of a strain analyzer system for sheet metal stamped parts based on an optical 3D digitizer

    NASA Astrophysics Data System (ADS)

    Carasusan, Eusebio; Canal, Fernando

    2003-05-01

    In this paper a new automatic strain analyzer system for sheet metal stamped parts is presented. This device is based on an optic 3D scanner working with structure white light, that performs measurements with high speed and accuracy. This new device can be a very useful tool in manufacturing industry.

  19. 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.

  20. An advanced constitutive model in the sheet metal forming simulation: the Teodosiu microstructural model and the Cazacu Barlat yield criterion

    NASA Astrophysics Data System (ADS)

    Alves, J. L.; Oliveira, M. C.; Menezes, L. F.

    2004-06-01

    Two constitutive models used to describe the plastic behavior of sheet metals in the numerical simulation of sheet metal forming process are studied: a recently proposed advanced constitutive model based on the Teodosiu microstructural model and the Cazacu Barlat yield criterion is compared with a more classical one, based on the Swift law and the Hill 1948 yield criterion. These constitutive models are implemented into DD3IMP, a finite element home code specifically developed to simulate sheet metal forming processes, which generically is a 3-D elastoplastic finite element code with an updated Lagrangian formulation, following a fully implicit time integration scheme, large elastoplastic strains and rotations. Solid finite elements and parametric surfaces are used to model the blank sheet and tool surfaces, respectively. Some details of the numerical implementation of the constitutive models are given. Finally, the theory is illustrated with the numerical simulation of the deep drawing of a cylindrical cup. The results show that the proposed advanced constitutive model predicts with more exactness the final shape (medium height and ears profile) of the formed part, as one can conclude from the comparison with the experimental results.

  1. Control of sheet-metal forming processes with piezoactuators in smart structures

    NASA Astrophysics Data System (ADS)

    Neugebauer, Reimund; Hoffmann, Michael; Roscher, Hans-Jürgen; Scheffler, Sören; Wolf, Klaus

    2006-03-01

    The most important project in sheet metal forming is streamlining the material flow since each rejects increases production costs. Using the multipoint cushion device together with an elastic blankholder makes it possible to actively manipulate the material flow in the flange range. This allows major enhancements in the deformation ratio, especially with the novel high strength materials in car body production. State-of-the-art is multiple draw pins to initiate the force on selected points on the blankholder. Admittedly, the cushion plate does not allow optimum force allocation because it is situated between hydraulic pressure rollers and draw pins. Replacing selected draw pins with piezoactuators for generating high forces allows systematic control of the force progression at critical forming areas during sheet draw-in. The system, consisting of the piezostack actuator, dynamometer and components for force initiation, was built as a compact unit with low resilience with the intension of using the inherent sensory properties of the piezostack actuator to measure force. Applying this principle throughout allows a reduction of hydraulic components which eventually lead to a less expensive one- point cushion device. Initial finding have already been arrived at in the context of a research project at the Fraunhofer Institute for Machine Tools and Forming Technology in Chemnitz, Germany in cooperation with a partner from the automobile industry. A draw pin was replaced ad hoc with a highly durable piezoactuator integrated in a force control cycle. The force progression during the sheet draw-in could be accurately adjusted according to a predetermined master curve. The master curve was taken up in the unregulated process and represents the quality criteria of a formed useable part. The real-time MATLAB Simulink XPC- Target simulation tool was used to develop an adjustment strategy that connects the specific signals of the press control (such as the tappet path, the die

  2. 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.

  3. Antischistosomal Activity of Oxindolimine-Metal Complexes

    PubMed Central

    Dario, Bruno S.; Couto, Ricardo A. A.; Pinto, Pedro L. S.; da Costa Ferreira, Ana M.

    2015-01-01

    In recent years, a class of oxindole-copper and -zinc complex derivatives have been reported as compounds with efficient proapoptotic activity toward different tumor cells (e.g., neuroblastomas, melanomas, monocytes). Here we assessed the efficacy of synthesized oxindole-copper(II), -zinc(II), and -vanadyl (VO2+) complexes against adult Schistosoma mansoni worms. The copper(II) complexes (50% inhibitory concentrations of 30 to 45 μM) demonstrated greater antischistosomal properties than the analogous zinc and vanadyl complexes regarding lethality, reduction of motor activity, and oviposition. PMID:26239976

  4. 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.

  5. 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.

  6. 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…

  7. Electron Capture Dissociation of Trivalent Metal Ion-Peptide Complexes

    PubMed Central

    Flick, Tawnya G.; Donald, William A.; Williams, Evan R.

    2013-01-01

    With electrospray ionization from aqueous solutions, trivalent metal ions readily adduct to small peptides resulting in formation of predominantly (peptide + MT – H)2+, where MT = La, Tm, Lu, Sm, Ho, Yb, Pm, Tb, or Eu, for peptides with molecular weights below ~1000 Da, and predominantly (peptide + MT)3+ for larger peptides. ECD of (peptide + MT – H)2+ results in extensive fragmentation from which nearly complete sequence information can be obtained, even for peptides for which only singly protonated ions are formed in the absence of the metal ions. ECD of these doubly charged complexes containing MT results in significantly higher electron capture efficiency and sequence coverage than peptide-divalent metal ion complexes that have the same net charge. Formation of salt-bridge structures in which the metal ion coordinates to a carboxylate group are favored even for (peptide + MT)3+. ECD of these latter complexes for large peptides results in electron capture by the protonation site located remotely from the metal ion and predominantly c/z fragments for all metals, except Eu3+, which undergoes a one electron reduction and only loss of small neutral molecules and b/y fragments are formed. These results indicate that solvation of the metal ion in these complexes is extensive, resulting in similar electrochemical properties of these metal ions both in the peptide environment and in water. PMID:23283726

  8. 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.

  9. 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.

  10. Compartmentation and complexation of metals in hyperaccumulator plants

    PubMed Central

    Leitenmaier, Barbara; Küpper, Hendrik

    2013-01-01

    Hyperaccumulators are being intensely investigated. They are not only interesting in scientific context due to their “strange” behavior in terms of dealing with high concentrations of metals, but also because of their use in phytoremediation and phytomining, for which understanding the mechanisms of hyperaccumulation is crucial. Hyperaccumulators naturally use metal accumulation as a defense against herbivores and pathogens, and therefore deal with accumulated metals in very specific ways of complexation and compartmentation, different from non-hyperaccumulator plants and also non-hyperaccumulated metals. For example, in contrast to non-hyperaccumulators, in hyperaccumulators even the classical phytochelatin-inducing metal, cadmium, is predominantly not bound by such sulfur ligands, but only by weak oxygen ligands. This applies to all hyperaccumulated metals investigated so far, as well as hyperaccumulation of the metalloid arsenic. Stronger ligands, as they have been shown to complex metals in non-hyperaccumulators, are in hyperaccumulators used for transient binding during transport to the storage sites (e.g., nicotianamine) and possibly for export of Cu in Cd/Zn hyperaccumulators [metallothioneins (MTs)]. This confirmed that enhanced active metal transport, and not metal complexation, is the key mechanism of hyperaccumulation. Hyperaccumulators tolerate the high amount of accumulated heavy metals by sequestering them into vacuoles, usually in large storage cells of the epidermis. This is mediated by strongly elevated expression of specific transport proteins in various tissues from metal uptake in the shoots up to the storage sites in the leaf epidermis. However, this mechanism seems to be very metal specific. Non-hyperaccumulated metals in hyperaccumulators seem to be dealt with like in non-hyperaccumulator plants, i.e., detoxified by binding to strong ligands such as MTs. PMID:24065978

  11. 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.

  12. 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.

  13. 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. PMID:22072941

  14. 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

  15. Long-term ice sheet-climate interactions under anthropogenic greenhouse forcing simulated with a complex Earth System Model

    NASA Astrophysics Data System (ADS)

    Vizcaíno, Miren; Mikolajewicz, Uwe; Gröger, Matthias; Maier-Reimer, Ernst; Schurgers, Guy; Winguth, Arne M. E.

    2008-11-01

    Several multi-century and multi-millennia simulations have been performed with a complex Earth System Model (ESM) for different anthropogenic climate change scenarios in order to study the long-term evolution of sea level and the impact of ice sheet changes on the climate system. The core of the ESM is a coupled coarse-resolution Atmosphere-Ocean General Circulation Model (AOGCM). Ocean biogeochemistry, land vegetation and ice sheets are included as components of the ESM. The Greenland Ice Sheet (GrIS) decays in all simulations, while the Antarctic ice sheet contributes negatively to sea level rise, due to enhanced storage of water caused by larger snowfall rates. Freshwater flux increases from Greenland are one order of magnitude smaller than total freshwater flux increases into the North Atlantic basin (the sum of the contribution from changes in precipitation, evaporation, run-off and Greenland meltwater) and do not play an important role in changes in the strength of the North Atlantic Meridional Overturning Circulation (NAMOC). The regional climate change associated with weakening/collapse of the NAMOC drastically reduces the decay rate of the GrIS. The dynamical changes due to GrIS topography modification driven by mass balance changes act first as a negative feedback for the decay of the ice sheet, but accelerate the decay at a later stage. The increase of surface temperature due to reduced topographic heights causes a strong acceleration of the decay of the ice sheet in the long term. Other feedbacks between ice sheet and atmosphere are not important for the mass balance of the GrIS until it is reduced to 3/4 of the original size. From then, the reduction in the albedo of Greenland strongly accelerates the decay of the ice sheet.

  16. Modulating electronic, magnetic and chemical properties of MoS2 monolayer sheets by substitutional doping with transition metals

    NASA Astrophysics Data System (ADS)

    Ma, Dongwei; Ju, Weiwei; Li, Tingxian; Zhang, Xiwei; He, Chaozheng; Ma, Benyuan; Tang, Yanan; Lu, Zhansheng; Yang, Zongxian

    2016-02-01

    Based on first-principles calculations, the effects of substitutional doping with transition-metal (TM) atoms (Co, Ni, Ru, Rh, Pd, Ir, Pt and Au) were investigated on the electronic structure, magnetic property and chemical activity of the molybdenum disulfide (MoS2) monolayer sheet. It is found that all the considered TM atoms are strongly bonded to the sulfur defects. The magnetic properties of MoS2 monolayer sheets can be modulated by embedding TM atoms. The introduced spin magnetic moments are 1.00, 1.00, 1.00, 0.99, and 2.00μB, respectively, for Ir, Rh, Co, Au and Ru doping. The electronic properties of MoS2 monolayer sheets are also significantly changed due to the induced impurity states in the band gap. The chemical activity of the TM-doped MoS2 monolayer sheet (TM-MoS2) is significantly enhanced compared with the undoped sheet. Most TM-MoS2 can strongly adsorb and thus effectively activate the adsorbed O2. It is proposed that the partially occupied d orbitals of the doped TM atoms localized in the vicinity of the Fermi level play a crucial role in adsorbing and activating the adsorbed O2. The adsorption of O2 can in turn modify the electronic structures and magnetic properties of TM-MoS2.

  17. Electronic and magnetic properties of monolayer SiC sheet doped with 3d-transition metals

    NASA Astrophysics Data System (ADS)

    Bezi Javan, Masoud

    2016-03-01

    We theoretically studied the electronic and magnetic properties of the monolayer SiC sheet doped by 3d transition-metal (TM) atoms. The structural properties, induced strain, electronic and magnetic properties were studied for cases that a carbon or silicon of the SiC sheet replaced with TM atoms. We found that the mount of induced strain to the lattice structure of the SiC sheet with substituting TM atoms is different for Si (TMSi) and C (TMC) sites as the TMSi structures have lower value of the strain. Also the TM atoms can be substituted in the lattice of the SiC sheet with different binding energy values for TMSi and TMC structures as the TMSi structures have higher value of the binding energies. Dependent to the structural properties, the TM doped SiC sheets show magnetic or nonmagnetic properties. We found that some structures such as MnSi, CuSi and CoC configurations have significant total magnetic moment about 3 μB.

  18. Impact Of Elastic Modulus Degradation On Springback In Sheet Metal Forming

    NASA Astrophysics Data System (ADS)

    Halilovič, Miroslav; Vrh, Marko; Štok, Boris

    2007-05-01

    Strain recovery after removal of forming loads, commonly defined as springback, is of great concern in sheet metal forming, in particular with regard to proper prediction of the final shape of the part. To control the problem a lot of work has been done, either by minimizing the springback on the material side or by increasing the estimation precision in corresponding process simulations. Unfortunately, by currently available software springback still cannot be adequately predicted, because most analyses of springback are using linear, isotropic and constant Young's modulus and Poisson's ratio. But, as it was measured and reported, none of it is true. The aim of this work is to propose an upgraded mechanical model which takes evolution of damage and related orthotropic stiffness degradation into account. Damage is considered by inclusion of ellipsoidal cavities, and their influence on the stiffness degradation is taken in accordance with the Mori-Tanaka theory, adopting the GTN model for plastic flow. In order to improve the numerical springback prediction, two major things are important: first, the correct evaluation of the stress-strain state at the end of the forming process, and second, correctness of the elastic properties used in the elastic relaxation analysis. Since in modelling of the forming process we adopt a damage constitutive model with orthotropic stiffness degradation considered, a corresponding damage parameters identification upon specific experimental tests data must be performed first, independently of the metal forming modelling. An improved identification of material parameters, which simultaneously considers tensile test results with different type of specimens and using neural network, is proposed. With regard to the case in which damage in material is neglected it is shown in the article how the springback of a formed part differs, when we take orthotropic damage evolution into consideration.

  19. Electrode Erosion Observed in Electrohydraulic Discharges Used in Pulsed Sheet Metal Forming

    NASA Astrophysics Data System (ADS)

    Bonnen, John J. F.; Golovashchenko, Sergey F.; Dawson, Scott A.; Mamutov, Alexander V.

    2013-12-01

    In this paper, we present results of electrode durability testing and electrode design in a pulsed electrohydraulic discharge environment. Pulsed electrohydraulic forming (EHF) is an electrodynamic process based upon high-voltage discharge of capacitors between two electrodes positioned in a fluid-filled chamber. EHF enables a more uniform distribution of strains, widens the formability window, and reduces elastic springback in the final part when compared to traditional sheet metal stamping. This extended formability allows the fabrication of panels of alternative high strength alloys that are otherwise difficult to make conventionally. It was found that, of the materials tested, steel electrodes not only survived the stresses encountered in the EHF chamber but also had lower erosion rates compared to molybdenum. Erosion rates were found to be constant for low carbon steel at 3.7 mm3/discharge, and they were high enough that the initial tip geometry was rapidly worn away and a more geometrically and thus electrically stable tip geometry had to be selected. Entrained air in the system had little influence on erosion rates but numerical modeling suggests that the erosion process takes place during the very initial stages of the pulse. Lastly, it was determined that the electrodes discussed in this paper can survive 2000 pulses.

  20. 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.

  1. 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.

  2. Approaches To Modelling Of Elastic Modulus Degradation In Sheet Metal Forming

    NASA Astrophysics Data System (ADS)

    Vrh, Marko; Halilovič, Miroslav; Štok, Boris

    2007-04-01

    Strain recovery after removal of forming loads, commonly defined as springback, is of great concern in sheet metal forming, in particular with regard to proper prediction of the final shape of the part. To control the problem a lot of work has been done, either by minimizing the springback on the material side or by increasing the estimation precision in corresponding process simulations. Unfortunately, by currently available software springback still cannot be adequately predicted, because most analyses of springback are using linear, isotropic and constant Young's modulus and Poisson's ratio. But, as it was measured and reported, none of it is true. The aim of this work is to propose an upgraded mechanical model which takes evolution of damage and related orthotropic stiffness degradation into account. Damage is considered by inclusion of ellipsoidal cavities, and their influence on the stiffness degradation is taken in accordance with the Mori-Tanaka theory, adopting the GTN model for plastic flow. With regard to the case in which damage in material is neglected it is shown in the article how the springback of a formed part differs, when we take orthotropic damage evolution into consideration.

  3. 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.

  4. π-Conjugated bis(terpyridine)metal complex molecular wires.

    PubMed

    Sakamoto, Ryota; Wu, Kuo-Hui; Matsuoka, Ryota; Maeda, Hiroaki; Nishihara, Hiroshi

    2015-11-01

    Bottom-up approaches have gained significant attention recently for the creation of nano-sized, ordered functional structures and materials. Stepwise coordination techniques, in which ligand molecules and metal sources are reacted alternatively, offer several advantages. Coordination bonds are stable, reversible, and self-assembling, and the resultant metal complex motifs may contain functionalities unique to their own characteristics. This review focuses on metal complex wire systems, specifically the bottom-up fabrication of linear and branched bis(terpyridine)metal complex wires on electrode surfaces. This system possesses distinct and characteristic electronic functionalities, intra-wire redox conduction and excellent long-range electron transport ability. This series of comprehensive studies exploited the customizability of bis(terpyridine)metal complex wires, including examining the influence of building blocks. In addition, simple yet effective electron transfer models were established for redox conduction and long-range electron transport. A fabrication technique for an ultra-long bis(terpyridine)metal complex wire is also described, along with its properties and functionalities. PMID:25864838

  5. π-Conjugated bis(terpyridine)metal complex molecular wires.

    PubMed

    Sakamoto, Ryota; Wu, Kuo-Hui; Matsuoka, Ryota; Maeda, Hiroaki; Nishihara, Hiroshi

    2015-11-01

    Bottom-up approaches have gained significant attention recently for the creation of nano-sized, ordered functional structures and materials. Stepwise coordination techniques, in which ligand molecules and metal sources are reacted alternatively, offer several advantages. Coordination bonds are stable, reversible, and self-assembling, and the resultant metal complex motifs may contain functionalities unique to their own characteristics. This review focuses on metal complex wire systems, specifically the bottom-up fabrication of linear and branched bis(terpyridine)metal complex wires on electrode surfaces. This system possesses distinct and characteristic electronic functionalities, intra-wire redox conduction and excellent long-range electron transport ability. This series of comprehensive studies exploited the customizability of bis(terpyridine)metal complex wires, including examining the influence of building blocks. In addition, simple yet effective electron transfer models were established for redox conduction and long-range electron transport. A fabrication technique for an ultra-long bis(terpyridine)metal complex wire is also described, along with its properties and functionalities.

  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. 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.

  8. 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.

  9. 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.

  10. Metal-free Ketjenblack incorporated nitrogen-doped carbon sheets derived from gelatin as oxygen reduction catalysts.

    PubMed

    Nam, Gyutae; Park, Joohyuk; Kim, Sun Tai; Shin, Dong-bin; Park, Noejung; Kim, Youngsik; Lee, Jang-Soo; Cho, Jaephil

    2014-01-01

    Electrocatalysts facilitating oxygen reduction reaction (ORR) are vital components in advanced fuel cells and metal-air batteries. Here we report Ketjenblack incorporated nitrogen-doped carbon sheets derived from gelatin and apply these easily scalable materials as metal-free electrocatalysts for ORR. These carbon nanosheets demonstrate highly comparable catalytic activity for ORR as well as better durability than commercial Vulcan carbon supported Pt catalysts in alkaline media. Physico-chemical characterization and theoretical calculations suggest that proper combination of graphitic and pyridinic nitrogen species with more exposed edge sites effectively facilitates a formation of superoxide, [O2(ad)](-), via one-electron transfer, thus increasing catalytic activities for ORR. Our results demonstrate a novel strategy to expose more nitrogen doped edge sites by irregular stacked small sheets in developing better electrocatalysts for Zn-air batteries. These desirable architectures are embodied by an amphiphlilic gelatin mediated compatible synthetic strategy between hydrophobic carbon and aqueous water.

  11. A reliability study of springback on the sheet metal forming process under probabilistic variation of prestrain and blank holder force

    NASA Astrophysics Data System (ADS)

    Mrad, Hatem; Bouazara, Mohamed; Aryanpour, Gholamreza

    2013-08-01

    This work deals with a reliability assessment of springback problem during the sheet metal forming process. The effects of operative parameters and material properties, blank holder force and plastic prestrain, on springback are investigated. A generic reliability approach was developed to control springback. Subsequently, the Monte Carlo simulation technique in conjunction with the Latin hypercube sampling method was adopted to study the probabilistic springback. Finite element method based on implicit/explicit algorithms was used to model the springback problem. The proposed constitutive law for sheet metal takes into account the adaptation of plastic parameters of the hardening law for each prestrain level considered. Rackwitz-Fiessler algorithm is used to find reliability properties from response surfaces of chosen springback geometrical parameters. The obtained results were analyzed using a multi-state limit reliability functions based on geometry compensations.

  12. 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.

  13. Metal-free Ketjenblack incorporated nitrogen-doped carbon sheets derived from gelatin as oxygen reduction catalysts.

    PubMed

    Nam, Gyutae; Park, Joohyuk; Kim, Sun Tai; Shin, Dong-bin; Park, Noejung; Kim, Youngsik; Lee, Jang-Soo; Cho, Jaephil

    2014-01-01

    Electrocatalysts facilitating oxygen reduction reaction (ORR) are vital components in advanced fuel cells and metal-air batteries. Here we report Ketjenblack incorporated nitrogen-doped carbon sheets derived from gelatin and apply these easily scalable materials as metal-free electrocatalysts for ORR. These carbon nanosheets demonstrate highly comparable catalytic activity for ORR as well as better durability than commercial Vulcan carbon supported Pt catalysts in alkaline media. Physico-chemical characterization and theoretical calculations suggest that proper combination of graphitic and pyridinic nitrogen species with more exposed edge sites effectively facilitates a formation of superoxide, [O2(ad)](-), via one-electron transfer, thus increasing catalytic activities for ORR. Our results demonstrate a novel strategy to expose more nitrogen doped edge sites by irregular stacked small sheets in developing better electrocatalysts for Zn-air batteries. These desirable architectures are embodied by an amphiphlilic gelatin mediated compatible synthetic strategy between hydrophobic carbon and aqueous water. PMID:24635744

  14. 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.

  15. Macrocyclic metal complexes for metalloenzyme mimicry and sensor development.

    PubMed

    Joshi, Tanmaya; Graham, Bim; Spiccia, Leone

    2015-08-18

    Examples of proteins that incorporate one or more metal ions within their structure are found within a broad range of classes, including oxidases, oxidoreductases, reductases, proteases, proton transport proteins, electron transfer/transport proteins, storage proteins, lyases, rusticyanins, metallochaperones, sporulation proteins, hydrolases, endopeptidases, luminescent proteins, iron transport proteins, oxygen storage/transport proteins, calcium binding proteins, and monooxygenases. The metal coordination environment therein is often generated from residues inherent to the protein, small exogenous molecules (e.g., aqua ligands) and/or macrocyclic porphyrin units found, for example, in hemoglobin, myoglobin, cytochrome C, cytochrome C oxidase, and vitamin B12. Thus, there continues to be considerable interest in employing macrocyclic metal complexes to construct low-molecular weight models for metallobiosites that mirror essential features of the coordination environment of a bound metal ion without inclusion of the surrounding protein framework. Herein, we review and appraise our research exploring the application of the metal complexes formed by two macrocyclic ligands, 1,4,7-triazacyclononane (tacn) and 1,4,7,10-tetraazacyclododecane (cyclen), and their derivatives in biological inorganic chemistry. Taking advantage of the kinetic inertness and thermodynamic stability of their metal complexes, these macrocyclic scaffolds have been employed in the development of models that aid the understanding of metal ion-binding natural systems, and complexes with potential applications in biomolecule sensing, diagnosis, and therapy. In particular, the focus has been on "coordinatively unsaturated" metal complexes that incorporate a kinetically inert and stable metal-ligand moiety, but which also contain one or more weakly bound ligands, allowing for the reversible binding of guest molecules via the formation and dissociation of coordinate bonds. With regards to mimicking

  16. Photodissociation Studies of Metal-Containing Clusters and Complexes

    NASA Astrophysics Data System (ADS)

    Pilgrim, Jeffrey Scott

    1995-01-01

    There have been two major areas of investigation for researchers working with laser ablation in molecular beams. The first area is the study of weakly-bound complexes. These complexes are bound by electrostatic interactions. In the present study the weakly bound interactions of the rare gases with the magnesium ion are investigated with electronic spectroscopy. The second major area is the study of metal and metal-containing clusters. Examples of previous investigations are the alkali metal clusters and the fullerenes. The present investigation is on metal -carbon clusters. The so-called metallo-carbohedrenes and metal-carbon nanocrystals are studied. Resonance enhanced photodissociation spectroscopy is used to obtain electronic excitation spectra of the Mg^+-rare gas species in the ultraviolet region. This investigation is facilitated by a reflectron time-of-flight mass spectrometer. The interaction of the rare gas with the metal ion is attributed to a "solvation" of the atomic ion transition. Simple bonding arguments predict that the excited state is more bound than the ground state for these complexes. This will result in a shift of the complex vibronic origin to lower energy from the atomic ion transition. This is exactly what is observed in the experiment with progressively larger shifts for the heavier rare gases. The electronic excitation spectra allow the vibrational frequencies and anharmonicities for these complexes to be obtained for the excited state. In turn, the excited state bond dissociation energies can be determined. Finally, conservation of energy allows calculation of the ground state bond dissociation energies. In the metal-carbon systems the stability of the metallo-carbohedrene, met-car, stoichiometry is shown to extend into the transition period at least to the iron group. Photodissociation with a 532 nm laser causes a loss of metal atoms for met-cars formed with first row transition metals and a loss of metal-carbon units for met

  17. 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.

  18. Complex Microfiltration Behavior of Metal Hydroxide Slurries

    SciTech Connect

    Shimskey, Rick W.; Schonewill, Philip P.; Daniel, Richard C.; Peterson, Reid A.

    2011-02-28

    Crossflow filtration is to be a key process in the treatment and disposal of approximately 60,000 metric tons of high-level waste stored at the Hanford Site in Richland, Washington. Pacific Northwest National Laboratory is assessing filter performance against waste simulant materials that mimic the chemical and physical properties of Hanford tank waste. Prior simulant studies indicate that waste filtration performance may be limited by pore and cake fouling. To limit the shutdown of waste treatment operations, the pre-treatment facility plans to recover filter flux loses from cake formation and filter fouling by frequently backpulsing the filter elements. The objective of the current research is to develop an understanding of the roles of cake and pore fouling and potential flux recovery through backpulsing of the filters for Hanford waste filtration operations. Metal hydroxide wastes were tested to examine the role of particle-filter interaction on filter performance.

  19. Metal Atom Lability in Polynuclear Complexes

    PubMed Central

    Eames, Emily V.; Sánchez, Raúl Hernández

    2013-01-01

    The asymmetric oxidation product [(PhL)Fe3(µ-Cl)]2 [PhLH6 = MeC(CH2NHPh-o-NHPh)3], where each trinuclear core is comprised of an oxidized diiron unit [Fe2]5+ and an isolated trigonal pyramidal ferrous site, reacts with MCl2 salts to afford heptanuclear bridged structures of the type (PhL)2Fe6M(µ-Cl)4(thf)2, where M = Fe or Co. Zero-field, 57Fe Mössbauer analysis revealed the Co resides within the trinuclear core subunits, not at the octahedral, halide-bridged MCl4(thf)2 position indicating Co migration into the trinuclear subunits has occurred. Reaction of [(PhL)Fe3(µ-Cl)]2 with CoCl2 (2 or 5 equivalents) followed by precipitation via addition of acetonitrile afforded trinuclear products where one or two irons, respectively, can be substituted within the trinuclear core. Metal atom substitution was verified by 1H NMR, 57Fe Mossbauer, single crystal X-ray diffraction, X-ray fluorescence, and magnetometry analysis. Spectroscopic analysis revealed that the Co atom(s) substitute into the oxidized dimetal unit ([M2]5+), while the M2+ site remains iron-substituted. Magnetic data acquired for the series are consistent with this analysis revealing the oxidized dimetal unit comprises a strongly coupled S = 1 unit ([FeCo]5+) or S = ½ ([Co2]5+) that is weakly antiferromagnetically coupled to the high spin (S = 2) ferrous site. The kinetic pathway for metal substitution was probed via reaction of [(PhL)Fe3(µ-Cl)]2 with isotopically enriched 57FeCl2(thf)2, the results of which suggest rapid equilibration of 57Fe into both the M2+ site and oxidized diiron site, achieving a 1:1 mixture. PMID:23642178

  20. Plasmonic Fano resonances in metallic nanorod complexes.

    PubMed

    Yang, Zhong-Jian; Hao, Zhong-Hua; Lin, Hai-Qing; Wang, Qu-Quan

    2014-05-21

    Plasmonic Fano resonances (FRs) in nanostructures have been extensively studied in recent years. Nanorod-based complexes for FRs have also attracted much attention. The basic optical properties and fabrication technology of different kinds of plasmonic nanorods have been greatly developed over the last several years. The mutipole plasmon resonances and their flexible adjustment ranges on nanorods make them promising for FR modifications and structure diversity. In this paper, we review some recently studied plasmonic nanorod based nanostructures for FRs, including single nanorods, dimers, mutipole rods and nanorod-nanoparticle hybrids. The corresponding applications of the FRs are also briefly discussed.

  1. Detection of cracks in metal sheets using pulsed laser generated ultrasound and EMAT detection.

    PubMed

    Dixon, S; Burrows, S E; Dutton, B; Fan, Y

    2011-01-01

    A pulsed Nd:YAG laser with an approximately Gaussian beam shape is directed onto the surface of an aluminium sheet at an energy density below which damage by laser ablation occurs, generating Lamb waves in the sheet. The laser beam is raster scanned across the surface of the sample. The Lamb waves travel radially outwards from the generation point and are detected some distance away by an electromagnetic acoustic transducer with sensitivity to in-plane displacements of the sheet. A number of static EMATs are located around the edges of the sheet, some distance from the generation point. The presence of a crack-like defect on the sheet can be detected by either a sudden change in the ultrasonic waveform or by an enhancement in the frequency content of the waveform when the laser beam illuminates directly onto the crack.

  2. 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.

  3. 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.

  4. Chemodynamics of aquatic metal complexes: from small ligands to colloids.

    PubMed

    Van Leeuwen, Herman P; Buffle, Jacques

    2009-10-01

    Recent progress in understanding the formation/dissociation kinetics of aquatic metal complexes with complexants in different size ranges is evaluated and put in perspective, with suggestions for further studies. The elementary steps in the Eigen mechanism, i.e., diffusion and dehydration of the metal ion, are reviewed and further developed. The (de)protonation of both the ligand and the coordinating metal ion is reconsidered in terms of the consequences for dehydration rates and stabilities of the various outer-sphere complexes. In the nanoparticulate size range, special attention is given to the case of fulvic ligands, for which the impact of electrostatic interactions is especially large. In complexation with colloidal ligands (hard, soft, and combination thereof) the diffusive transport of metal ions is generally a slower step than in the case of complexation with small ligands in a homogeneous solution. The ensuing consequences for the chemodynamics of colloidal complexes are discussed in detail and placed in a generic framework, encompassing the complete range of ligand sizes.

  5. 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

  6. 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.

  7. Electrochemical response of metal complexes in homogeneous solution under photoirradiation

    PubMed Central

    Fukatsu, Arisa; Kondo, Mio; Okamura, Masaya; Yoshida, Masaki; Masaoka, Shigeyuki

    2014-01-01

    The electrochemical detection of metal complexes in the photoexcited state is important for understanding photoinduced electron transfer (PET) processes, which play a central role in photo-energy conversion systems. In general, however, the redox potentials of excited states have been indirectly estimated by a combination of spectroscopic properties and ground-state redox potentials. To establish a simple method for directly determining the redox potentials of the photoexcited states of metal complexes, electrochemical measurements under several conditions were performed. The electrochemical response was largely influenced not only by the generation of photoexcited molecules but also by the convection induced by photoirradiation, even when the global temperature of the sample solution was unchanged. The suppression of these unfavourable electrochemical responses was successfully achieved by adopting well-established electrochemical techniques. Furthermore, as an initial demonstration, the photoexcited state of a Ru-based metal complex was directly detected, and its redox potential was determined using a thin layer electrochemical method. PMID:24937471

  8. An Alkali Metal-Capped Cerium(IV) Imido Complex.

    PubMed

    Solola, Lukman A; Zabula, Alexander V; Dorfner, Walter L; Manor, Brian C; Carroll, Patrick J; Schelter, Eric J

    2016-06-01

    Structurally authenticated, terminal lanthanide-ligand multiple bonds are rare and expected to be highly reactive. Even capped with an alkali metal cation, poor orbital energy matching and overlap of metal and ligand valence orbitals should result in strong charge polarization within such bonds. We expand on a new strategy for isolating terminal lanthanide-ligand multiple bonds using cerium(IV) complexes. In the current case, our tailored tris(hydroxylaminato) ligand framework, TriNOx(3-), provides steric protection against ligand scrambling and metal complex oligomerization and electronic protection against reduction. This strategy culminates in isolation of the first formal Ce═N bonded moiety in the complex [K(DME)2][Ce═N(3,5-(CF3)2C6H3)(TriNOx)], whose Ce═N bond is the shortest known at 2.119(3) Å. PMID:27163651

  9. 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.

  10. 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.

  11. A comparative theoretical study of metal functionalized carbon nanocones and carbon nanocone sheets as potential hydrogen storage materials.

    PubMed

    Shalabi, A S; Soliman, K A; Taha, H O

    2014-09-28

    The hydrogen storage of Ti functionalized carbon nanocones and carbon nanocone sheets is investigated by using the state-of-the-art density functional theory calculations. The Ti atom prefers to bind at the hollow site of the hexagonal ring. The average adsorption energies corrected for dispersion forces are -0.54 and -0.39 eV per hydrogen molecule. With no metal clustering, the system gravimetric capacities are expected to be as large as 9.31 and 11.01 wt%. The hydrogen storage reactions are characterized in terms of simulated infrared spectra, projected densities of states, kinetics, and statistical thermodynamics. The free energies and enthalpies of the Ti functionalized carbon nanocone meet the ultimate targets of the Department of Energy for all temperatures and pressures. The closest reactions to zero free energy occur at 378.15 K/2.961 atm for carbon nanocones and 233.15 K/2.961 atm for carbon nanocone sheets. The translational component is found to exert a dominant effect on the total entropy change with temperature. More promising thermodynamics are assigned to the hydrogenation of Ti functionalized carbon nanocone sheets at 233.15 K. As the temperature is increased, the lifetimes of the hydrogen molecules adsorbed at the surface drop and the rate constants increase. At fixed pressure, the rate constants of hydrogenation of Ti functionalized carbon nanocones are smaller than those of Ti functionalized carbon nanocone sheets, while the lifetimes are greater.

  12. 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

  13. Competitive complexation of metal ions with humic substances.

    PubMed

    Zhou, Ping; Yan, Hui; Gu, Baohua

    2005-03-01

    The surface complexation model was applied to simulate the competitive complexation of Ni, Ca and Al with humic substances. The presence of two types of binding sites in humic acid, carboxylic and phenolic functional groups, were assumed at both low and high pH conditions. Potentiometric titrations were used to characterize the intrinsic acidity constants of the two binding sites and their concentrations. It was found that the diffuse-layer model (DLM) could fit the experimental data well under different experimental conditions. Ni and Ca ions strongly compete with each other for reactions with the humic acid but Al showed little influence on the complexation of either Ni or Ca due to its hydrolysis and precipitation at pH approximately 5. The surface complexation constants determined from the mono-element systems were compared with those obtained from the multiple-element system (a mixture of the three metal ions). Results indicate little changes in the intrinsic surface complexation constants. Modeling results also indicate that high concentrations of Ca in the contaminated groundwater could strongly inhibit the complexation of Ni ions whereas an increase in pH and the humic concentration could attenuate such competitive interactions. The present study suggests that the surface complexation model could be useful in predicting interactions of the metal ions with humic substances and potentially aid in the design of remediation strategies for metal-contaminated soil and groundwater.

  14. 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.

  15. Properties- and applications of quasicrystals and complex metallic alloys.

    PubMed

    Dubois, Jean-Marie

    2012-10-21

    This article aims at an account of what is known about the potential for applications of quasicrystals and related compounds, the so-called family of Complex Metallic Alloys (CMAs‡). Attention is focused at aluminium-based CMAs, which comprise a large number of crystalline compounds and quasicrystals made of aluminium alloyed with transition metals (like Fe or Cu) or normal metals like Mg. Depending on composition, the structural complexity varies from a few atoms per unit cell up to thousands of atoms. Quasicrystals appear then as CMAs of ultimate complexity and exhibit a lattice that shows no periodicity anymore in the usual 3-dimensional space. Properties change dramatically with lattice complexity and turn the metal-type behaviour of simple Al-based crystals into a far more complex behaviour, with a fingerprint of semi-conductors that may be exploited in various applications, potential or realised. An account of the ones known to the author is given in the light of the relevant properties, namely light absorption, reduced adhesion and friction, heat insulation, reinforcement of composites for mechanical devices, and few more exotic ones. The role played by the search for applications of quasicrystals in the development of the field is briefly addressed in the concluding section.

  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. PMID:22179333

  17. 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.

  18. Metal ion coordination, conditional stability constants, and solution behavior of chelating surfactant metal complexes.

    PubMed

    Svanedal, Ida; Boija, Susanne; Almesåker, Ann; Persson, Gerd; Andersson, Fredrik; Hedenström, Erik; Bylund, Dan; Norgren, Magnus; Edlund, Håkan

    2014-04-29

    Coordination complexes of some divalent metal ions with the DTPA (diethylenetriaminepentaacetic acid)-based chelating surfactant 2-dodecyldiethylenetriaminepentaacetic acid (4-C12-DTPA) have been examined in terms of chelation and solution behavior. The headgroup of 4-C12-DTPA contains eight donor atoms that can participate in the coordination of a metal ion. Conditional stability constants for five transition metal complexes with 4-C12-DTPA were determined by competition measurements between 4-C12-DTPA and DTPA, using electrospray ionization mass spectrometry (ESI-MS). Small differences in the relative strength between the coordination complexes of DTPA and 4-C12-DTPA indicated that the hydrocarbon tail only affected the chelating ability of the headgroup to a limited extent. The coordination of Cu(2+) ions was investigated in particular, using UV-visible spectroscopy. By constructing Job's plots, it was found that 4-C12-DTPA could coordinate up to two Cu(2+) ions. Surface tension measurements and NMR diffusometry showed that the coordination of metal ions affected the solution behavior of 4-C12-DTPA, but there were no specific trends between the studied divalent metal complexes. Generally, the effects of the metal ion coordination could be linked to the neutralization of the headgroup charge of 4-C12-DTPA, and the resulting reduced electrostatic repulsions between adjacent surfactants in micelles and monolayers. The pH vs concentration plots, on the other hand, showed a distinct difference between 4-C12-DTPA complexes of the alkaline earth metals and the transition metals. This was explained by the difference in coordination between the two groups of metal ions, as predicted by the hard and soft acid and base (HSAB) theory.

  19. Metal ion coordination, conditional stability constants, and solution behavior of chelating surfactant metal complexes.

    PubMed

    Svanedal, Ida; Boija, Susanne; Almesåker, Ann; Persson, Gerd; Andersson, Fredrik; Hedenström, Erik; Bylund, Dan; Norgren, Magnus; Edlund, Håkan

    2014-04-29

    Coordination complexes of some divalent metal ions with the DTPA (diethylenetriaminepentaacetic acid)-based chelating surfactant 2-dodecyldiethylenetriaminepentaacetic acid (4-C12-DTPA) have been examined in terms of chelation and solution behavior. The headgroup of 4-C12-DTPA contains eight donor atoms that can participate in the coordination of a metal ion. Conditional stability constants for five transition metal complexes with 4-C12-DTPA were determined by competition measurements between 4-C12-DTPA and DTPA, using electrospray ionization mass spectrometry (ESI-MS). Small differences in the relative strength between the coordination complexes of DTPA and 4-C12-DTPA indicated that the hydrocarbon tail only affected the chelating ability of the headgroup to a limited extent. The coordination of Cu(2+) ions was investigated in particular, using UV-visible spectroscopy. By constructing Job's plots, it was found that 4-C12-DTPA could coordinate up to two Cu(2+) ions. Surface tension measurements and NMR diffusometry showed that the coordination of metal ions affected the solution behavior of 4-C12-DTPA, but there were no specific trends between the studied divalent metal complexes. Generally, the effects of the metal ion coordination could be linked to the neutralization of the headgroup charge of 4-C12-DTPA, and the resulting reduced electrostatic repulsions between adjacent surfactants in micelles and monolayers. The pH vs concentration plots, on the other hand, showed a distinct difference between 4-C12-DTPA complexes of the alkaline earth metals and the transition metals. This was explained by the difference in coordination between the two groups of metal ions, as predicted by the hard and soft acid and base (HSAB) theory. PMID:24702119

  20. Coinage metal complexes supported by the tri- and tetraphosphine ligands.

    PubMed

    Dau, Minh Thuy; Shakirova, Julia R; Karttunen, Antti J; Grachova, Elena V; Tunik, Sergey P; Melnikov, Alexey S; Pakkanen, Tapani A; Koshevoy, Igor O

    2014-05-01

    A series of tri- and tetranuclear phosphine complexes of d(10) metal ions supported by the polydentate ligands, bis(diphenylphosphinomethyl)phenylphosphine (PPP) and tris(diphenylphosphinomethyl)phosphine (PPPP), were synthesized. All the compounds under study, [AuM2(PPP)2](3+) (M = Au (1), Cu (2), Ag (3)), [M4(PPPP)2](4+) (M = Ag (4), Au (5)), [AuAg3(PPPP)2](4+) (6), and [Au2Cu2(PPPP)2(NCMe)4](4+) (7), were characterized crystallographically. The trinuclear clusters 1-3 contain a linear metal core, while in the isostructural tetranuclear complexes 4-6 the metal framework has a plane star-shaped arrangement. Cluster 7 adopts a structural motif that involves a digold unit bridged by two arms of the PPPP phosphines and decorated two spatially separated Cu(I) ions chelated by the remaining P donors. The NMR spectroscopic investigation in DMSO solution revealed the heterometallic clusters 2, 3, and 6 are stereochemically nonrigid and undergo reversible metal ions redistribution between several species, accompanied by their solvation-desolvation. The complexes 1-3 and 5-7 exhibit room temperature luminescence in the solid state (Φem = 6-64%) in the spectral region from 450 to 563 nm. The phosphorescence observed originates from the triplet excited states, determined by the metal cluster-centered dσ* → pσ transitions. PMID:24750114

  1. 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

  2. Epidotisation and fluid flow in sheeted dyke complex : new field and experimental constraints

    NASA Astrophysics Data System (ADS)

    Coelho, Gabriel; Sizaret, Stanislas; Arbaret, Laurent; Branquet, Yannick; Champallier, Rémi

    2013-04-01

    Hydrothermal system in oceanic crust is usually studied via dredge samples and drilled holes but their equivalent are also found in ophiolitic complexes (Oman, Cyprus). In the deepest zone, the fluids react with the sheeted diabase dikes at 400°C and 400 bars to form epidosites by enrichment in epidote and quartz [1]. Mineralogy and chemistry of epidosites have been widely studied on fields [1] and hydrology is generally studied using numerical models [2]. However, the relations and the timing of the emplacement of diabase dikes, their alteration in epidosite and the regional deformation remain unclear. We performed experiments on diabase sampled in the Troodos complex (Cyprus), 1) to stress the P-T-fO2-fluid composition conditions of the reaction of epidotisation and, 2) to quantify interrelations between the permeability and the epidotisation during deformation. In Troodos, we observed two major types of epidosite: 1) a pervasive epidosite in the core of dikes and a banding which is parallel to chilled margins and, 2) assemblages of epidote and quartz as alteration fronts in cooling joints or in the form of veins cross-cutting non-epidotised dikes. This last type of epidotisation clearly appears to be a hydrothermal veining process. We synthesized epidote in a static autoclave with external heating at 500°C and 2500 bars. Epidote was formed by the following reaction: 6 albite + 2 hematite + anorthite + 7 Ca2+ + 6 H2O → 4 epidote + 8 quartz + 6 Na+ + 8 H+. The calculated variation of the molar volume is about -3% (creation of porosity). Two parameters are essential to synthesize epidote from diabase: the oxygen fugacity and the composition of the fluid (enriched in Ca and Fe). However, there is an obvious problem of nucleation at 400°C and 400 bars. In order to understand how fluid flows throughout sheeted dikes, in situ measurements of permeability during coaxial deformation have been performed in a Paterson apparatus by infiltration of Argon and water. The

  3. [Applications of metal ions and their complexes in medicine I].

    PubMed

    Nagy, László; Csintalan, Gabriella; Kálmán, Eszter; Sipos, Pál; Szvetnik, Attila

    2003-01-01

    The "inorganic medical chemistry" is a rapidly developing field with enormous potential for applications, which offers new possibilities to the pharmaceutical industry. For example, the titanocene dichloride is already in clinical use, and antimetastatic activity of a range of Ru(III) complexes is also well established. There are ways to minimize the toxicity of Gd(III) complexes and therefore they can be safely injected as MRI contrast agents. The so called "ligand design" allows paramagnetic ions to be targeted to specific organs. Such designed ligands also enable the targeting of radiodiagnostic (99mTc) and radiotherapeutic (186Re) isotopes. There is a significant progress in understanding the coordination chemistry and biochemistry of metal ion(s) containing complexes such as Au antiarthritic and Bi antiulcer drugs. Further, currently developing areas include Mn (SOD mimics), V (insulin mimics), Ru (NO scavengers), Ln-based photosensitizers, metal-targeted organic agents and the Fe overload. The expanding knowledge of the role of metals in biochemistry is expected to provide scope for the design of new drugs in many other areas too, for example neuropharmaceutical and antiaffective agents. Progress in coordination chemistry is strongly dependent on understanding not only the thermodynamics of reactions, but also the kinetics of metal complexes under biologically relevant conditions.

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

    DOE PAGES

    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 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

  5. Metal Complexes as Color Indicators for Solvent Parameters.

    ERIC Educational Resources Information Center

    Soukup, Rudolf W.; Schmid, Roland

    1985-01-01

    Although indicators are omnipresent tools in aqueous chemistry, they have not been used extensively to assign solvent properties in nonaqueous systems. Therefore, recent research into a system of metal complexes that can be used to assign donor and acceptor numbers to nonaqueous solvents is summarized. Pertinent experiments are also described. (JN)

  6. 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.

  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. 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.

  9. 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

  10. N-Heterocyclic carbene metal complexes: photoluminescence and applications.

    PubMed

    Visbal, Renso; Gimeno, M Concepción

    2014-05-21

    This review covers the advances made in the synthesis of luminescent transition metal complexes containing N-heterocyclic carbene (NHC) ligands. The presence of a high field strength ligand such as an NHC in the complexes gives rise to high energy emissions, and consequently, to the desired blue colour needed for OLED applications. Furthermore, the great versatility of NHC ligands for structural modifications, together with the use of other ancillary ligands in the complex, provides numerous possibilities for the synthesis of phosphorescent materials, with emission colours over the entire visible spectra and potential future applications in fields such as photochemical water-splitting, chemosensors, dye-sensitised solar cells, oxygen sensors, and medicine.

  11. Metal complexes of mycobactin P and of desferrisideramines

    PubMed Central

    Snow, G. A.

    1969-01-01

    Crystalline gallium mycobactin P and chromic mycobactin P have been prepared. The chromic compound, unlike other metallic complexes of mycobactin P, does not detectably exchange its metal with ferric iron; it competitively antagonizes the growth-promoting action of mycobactin P towards Mycobacterium johnei. Mycobactin P, desferrioxamine B and desferrichrysin form coloured 1:1 complexes with ammonium vanadate. The vanadyl complexes of the water-soluble desferrisideramines are formed in aqueous solution. Two distinct forms occur at pH7 and pH3; these are slowly interconvertible when the pH is changed. The complexes show other changes at lower pH values; unlike other metallic desferrisideramine complexes, the vanadyl compounds do not dissociate even in the strongest acids, but dissociate above pH9. Their properties have been studied spectrophotometrically, by electrophoresis and by electrometric titration. The affinity of mycobactin for ferric iron is greater than that of desferrioxamine B under two different conditions of measurement. PMID:5378379

  12. Nd:YAG Laser Welding of Sheet Metal Assembly: Transformation Induced Volume Strain Affect on Elastoplastic Model

    NASA Astrophysics Data System (ADS)

    Seang, C.; David, A. K.; Ragneau, E.

    This study presents the effect of transformation induced volume strain on the thermo-elastoplastic model in the simulation of Nd: YAG laser welding process applied for thin sheet metal dual phases steel DP600. The metallurgical phase transformations during heating and during cooling are used as the thermal expansion dependent parameters. The effect of transformation induced volumetric strain was identified where the comparisons of the elastoplastic model with and without metallurgical effect are based on the global distribution of residual stresses such as the longitudinal residual stresses and the transverse residual stresses.

  13. Ternary metal complexes of guaifenesin drug: Synthesis, spectroscopic characterization and in vitro anticancer activity of the metal complexes.

    PubMed

    Mahmoud, W H; Mahmoud, N F; Mohamed, G G; El-Sonbati, A Z; El-Bindary, A A

    2015-01-01

    The coordination behavior of a series of transition metal ions named Cr(III), Fe(III), Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) with a mono negative tridentate guaifenesin ligand (GFS) (OOO donation sites) and 1,10-phenanthroline (Phen) is reported. The metal complexes are characterized based on elemental analyses, IR, (1)H NMR, solid reflectance, magnetic moment, molar conductance, UV-vis spectral studies, mass spectroscopy, ESR, XRD and thermal analysis (TG and DTG). The ternary metal complexes were found to have the formulae of [M(GFS)(Phen)Cl]Cl·nH2O (M=Cr(III) (n=1) and Fe(III) (n=0)), [M(GFS)(Phen)Cl]·nH2O (M=Mn(II) (n=0), Zn(II) (n=0) and Cu(II) (n=3)) and [M(GFS)(Phen)(H2O)]Cl·nH2O (M=Co(II) (n=0), Ni(II) (n=0) and Cd(II) (n=4)). All the chelates are found to have octahedral geometrical structures. The ligand and its ternary chelates are subjected to thermal analyses (TG and DTG). The GFS ligand, in comparison to its ternary metal complexes also was screened for their antibacterial activity on gram positive bacteria (Bacillus subtilis and Staphylococcus aureus), gram negative bacteria (Escherichia coli and Neisseria gonorrhoeae) and for in vitro antifungal activity against (Candida albicans). The activity data show that the metal complexes have antibacterial and antifungal activity more than the parent GFS ligand. The complexes were also screened for its in vitro anticancer activity against the Breast cell line (MFC7) and the results obtained show that they exhibit a considerable anticancer activity. PMID:26067934

  14. Comparison of Conventional Deep Drawing, Hydromechanical Deep-Drawing and High Pressure Sheet Metal Forming by Numerical Experiments

    NASA Astrophysics Data System (ADS)

    Önder, I. Erkan; Tekkaya, A. Erman

    2005-08-01

    Increasing use of new technologies in automotive and aircraft applications requires intensive research and developments on sheet metal forming processes. This study focuses on the assessment of sheet hydroforming, hydro-mechanical deep drawing and conventional deep-drawing processes by performing a systematic analysis by numerical simulations. Circular, elliptic, rectangular and square cross-section cups have been selected for the geometry spectrum. Within the range of each cross section, depth, drawing ratio and fillet radii have been altered systematically. St14 stainless steel has been used as the material throughout the study. The deformation behavior has been described by an elasto-plastic material model and all numerical simulations have been carried out by using a dynamic-explicit commercial finite element code. During the analyses each workpiece is produced by the three competing processes. The analyses results such as sheet thickness distribution, necking, forming of radii etc., are used for assessing the success of each forming process alternative. The analyses revealed that depending on the workpiece geometry and dimensional properties certain processes are preferable for obtaining satisfactory products. The process windows for each process have been established based on the analyzed parameters of the three different product geometries. This data is expected to be useful for selecting the appropriate production process for a given workpiece geometry.

  15. Experimental Characterization of Sheet Metal Deformation During Electro-Hydraulic Forming

    SciTech Connect

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

    2011-11-01

    This manuscripts reports results of the last 2-3 years work pertaining to DOE-OVT funded project on pulse-pressure forming of light-weight materials. We report experimental results of electrohydraulically formed sheets where data is determined using a pair of high-speed cameras and analyzed using a digital image correlation technique. These results are relevant to the formability of sheet materials and of importance to the automotive industry. To the authors’ knowledge, such results have not been published in the literature.

  16. 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.

  17. 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.

  18. Deposition of Metal Oxide Films from Metal-EDTA Complexes by Flame Spray Technique

    NASA Astrophysics Data System (ADS)

    Komatsu, Keiji; Sekiya, Tetsuo; Toyama, Ayumu; Hasebe, Yasuhiro; Nakamura, Atsushi; Noguchi, Masahiro; Li, Yu; Ohshio, Shigeo; Akasaka, Hiroki; Muramatsu, Hiroyuki; Saitoh, Hidetoshi

    2014-06-01

    R2O3 (R = Y, Eu, Er) metal oxides were synthesized from metal-ethylenediaminetetraacetic acid (EDTA) complexes using a flame spray technique. As this technique enables high deposition rates, films with thickness of several tens of micrometers were obtained. Films of yttria, europia, and erbia phase were synthesized on stainless-steel substrates with reaction assistance by H2-O2 combustion gas. The oxide films consisted of the desired crystalline phase with micropores. The porosity of the films was in the range of 6-15%, varying with the metal used. These results suggest that the true density of the metal oxide obtained from metal-EDTA powder through the thermal reaction process plays an important role in achieving film with the desired porosity.

  19. Functional Characterization and Metal Ion Specificity of the Metal-Citrate Complex Transporter from Streptomyces coelicolor▿

    PubMed Central

    Lensbouer, Joshua J.; Patel, Ami; Sirianni, Joseph P.; Doyle, Robert P.

    2008-01-01

    Secondary transporters of citrate in complex with metal ions belong to the bacterial CitMHS family, about which little is known. The transport of metal-citrate complexes in Streptomyces coelicolor has been investigated. The best cofactor for citrate uptake in Streptomyces coelicolor is Fe3+, but uptake was also noted for Ca2+, Pb2+, Ba2+, and Mn2+. Uptake was not observed with the Mg2+, Ni2+, or Co2+ cofactor. The transportation of iron- and calcium-citrate makes these systems unique among the CitMHS family members reported to date. No complementary uptake akin to that observed for the CitH (Ca2+, Ba2+, Sr2+) and CitM (Mg2+, Ni2+, Mn2+, Co2+, Zn2+) systems of Bacillus subtilis was noted. Competitive experiments using EGTA confirmed that metal-citrate complex formation promoted citrate uptake. Uptake of free citrate was not observed. The open reading frame postulated as being responsible for the metal-citrate transport observed in Streptomyces coelicolor was cloned and overexpressed in Escherichia coli strains with the primary Fe3+-citrate transport system (fecABCDE) removed. Functional expression was successful, with uptake of Ca2+-citrate, Fe3+-citrate, and Pb2+-citrate observed. No free-citrate transport was observed in IPTG (isopropyl-β-d-thiogalactopyranoside)-induced or -uninduced E. coli. Metabolism of the Fe3+-citrate and Ca2+-citrate complexes, but not the Pb2+-citrate complex, was observed. Rationalization is based on the difference in metal-complex coordination upon binding of the metal by citrate. PMID:18556792

  20. 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.

  1. Development of a laser-speckle-based measurement principle for the evaluation of mechanical deformation of stacked metal sheets

    NASA Astrophysics Data System (ADS)

    Halder, Clemens; Thurner, Thomas; Mair, Mathias

    2014-05-01

    Stacks of metal plates are widely used in electrical motors, transformers and generators to reduce for eddy current loss in their magnetic circuit. To model the mechanical behavior of such special material structures a profound knowledge of the underlying physical processes is needed. This paper describes a highly specialized optical sensor system utilizing the laser-speckle-effect for non-contacting strain and displacement measurements of stacked metal plates. In order to gain insights into the mechanical changes of stacked metal structures during defined mechanical load, a certain kind of spatially resolving digital laser speckle photography has been used to measure displacements between individual layers of the stacked metal sheets at high resolution. The developed speckle template matching algorithm takes into account for the very special surface structure and the given loading behavior. The sensor system is capable of acquiring displacement fields with a resolution in the order of a single micron at video rate and beyond, enabling the real time observation of load experiments on stacked metal plate structures.

  2. A laser-sheet flow visualization technique for the large wind tunnels of the National Full-Scale Aerodynamics Complex

    NASA Technical Reports Server (NTRS)

    Reinath, M. S.; Ross, J. C.

    1990-01-01

    A flow visualization technique for the large wind tunnels of the National Full Scale Aerodynamics Complex (NFAC) is described. The technique uses a laser sheet generated by the NFAC Long Range Laser Velocimeter (LRLV) to illuminate a smoke-like tracer in the flow. The LRLV optical system is modified slightly, and a scanned mirror is added to generate the sheet. These modifications are described, in addition to the results of an initial performance test conducted in the 80- by 120-Foot Wind Tunnel. During this test, flow visualization was performed in the wake region behind a truck as part of a vehicle drag reduction study. The problems encountered during the test are discussed, in addition to the recommended improvements needed to enhance the performance of the technique for future applications.

  3. A laser-sheet flow visualization technique for the large wind tunnels of the National Full-Scale Aerodynamics Complex

    NASA Astrophysics Data System (ADS)

    Reinath, M. S.; Ross, J. C.

    1990-09-01

    A flow visualization technique for the large wind tunnels of the National Full Scale Aerodynamics Complex (NFAC) is described. The technique uses a laser sheet generated by the NFAC Long Range Laser Velocimeter (LRLV) to illuminate a smoke-like tracer in the flow. The LRLV optical system is modified slightly, and a scanned mirror is added to generate the sheet. These modifications are described, in addition to the results of an initial performance test conducted in the 80- by 120-Foot Wind Tunnel. During this test, flow visualization was performed in the wake region behind a truck as part of a vehicle drag reduction study. The problems encountered during the test are discussed, in addition to the recommended improvements needed to enhance the performance of the technique for future applications.

  4. Binding energies of exciton complexes in transition metal dichalcogenide monolayers and effect of dielectric environment

    NASA Astrophysics Data System (ADS)

    Kylänpää, Ilkka; Komsa, Hannu-Pekka

    2015-11-01

    Excitons, trions, biexcitons, and exciton-trion complexes in two-dimensional transition metal dichalcogenide sheets of MoS2, MoSe2, MoTe2, WS2, and WSe2 are studied by means of density functional theory and path-integral Monte Carlo method in order to accurately account for the particle-particle correlations. In addition, the effect of dielectric environment on the properties of these exciton complexes is studied by modifying the effective interaction potential between particles. Calculated exciton and trion binding energies are consistent with previous experimental and computational studies, and larger systems such as biexciton and exciton-trion complex are found highly stable. Binding energies of biexcitons are similar to or higher than those of trions, but the binding energy of the trion depends significantly stronger on the dielectric environment than that of biexciton. Therefore, as a function of an increasing dielectric constant of the environment the exciton-trion complex "dissociates" to a biexciton rather than to an exciton and a trion.

  5. Equilibrium modeling of trace metal transport from Duluth complex rockpile

    SciTech Connect

    Kelsey, P.D.; Klusman, R.W.; Lapakko, K.

    1996-12-31

    Geochemical modeling was used to predict weathering processes and the formation of trace metal-adsorbing secondary phases in a waste rock stockpile containing Cu-Ni ore mined from the Duluth Complex, MN. Amorphous ferric hydroxide was identified as a secondary phase within the pile, from observation and geochemical modeling of the weathering process. Due to the high content of cobalt, copper, nickel, and zinc in the primary minerals of the waste rock and in the effluent, it was hypothesized that the predicted and observed precipitant ferric hydroxide would adsorb small quantities of these trace metals. This was verified using sequential extractions and simulated using adsorption geochemical modeling. It was concluded that the trace metals were adsorbed in small quantities, and adsorption onto the amorphous ferric hydroxide was in decreasing order of Cu > Ni > Zn > Co. The low degree of adsorption was due to low pH water and competition for adsorption sites with other ions in solution.

  6. 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.

  7. Growth of Hollow Transition Metal (Fe, Co, Ni) Oxide Nanoparticles on Graphene Sheets through Kirkendall Effect as Anodes for High-Performance Lithium-Ion Batteries.

    PubMed

    Yu, Xianbo; Qu, Bin; Zhao, Yang; Li, Chunyan; Chen, Yujin; Sun, Chunwen; Gao, Peng; Zhu, Chunling

    2016-01-26

    A general strategy based on the nanoscale Kirkendall effect has been developed to grow hollow transition metal (Fe, Co or Ni) oxide nanoparticles on graphene sheets. When applied as lithium-ion battery anodes, these hollow transition metal oxide-based composites exhibit excellent electrochemical performance, with high reversible capacities and long-term stabilities at a high current density, superior to most transition metal oxides reported to date.

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

    SciTech Connect

    Trovitch, R. J.; John, K. D.; Martin, R. L.; Obrey, S. J.; Sattelberger, A. P.; Scott, B. L.; Baker, R. T.; LANL; Univ. of Ottawa

    2009-01-01

    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}-{eta}{sup 1}, {eta}{sup 3} bonding mode; theoretical studies elucidate the roles of the {sigma}- and {pi}-donor ligands in the interplay of metal-allyl and metal-metal bonding.

  9. 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.

  10. Mono- and Dinuclear Macrocyclic Calcium Complexes as Platforms for Mixed-Metal Complexes and Clusters.

    PubMed

    Connolly, Emma A; Leeland, James W; Love, Jason B

    2016-01-19

    Mono- and dinuclear calcium complexes of the Schiff-base macrocycles H4L have been prepared and characterized spectroscopically and crystallographically. In the formation of Ca(THF)2(H2L(1)), Ca2(THF)2(μ-THF)(L(1)), and Ca2(THF)4(L(2)), the ligand framework adopts a bowl-shaped conformation instead of the conventional wedge, Pacman-shaped structure as seen with the anthracenyl-hinged complex Ca2(py)5(L(3)). The mononuclear calcium complex Ca(THF)2(H2L(1)) reacts with various equivalents of LiN(SiMe3)2 to form calcium/alkali metal clusters and dinuclear transition metal complexes when reacted subsequently with transition metal salts. The dinuclear calcium complex Ca2(THF)2(μ-THF)(L(1)), when reacted with various equivalents of NaOH, is shown to act as a platform for the formation of calcium/alkali metal hydroxide clusters, displaying alternate wedged and bowl-shaped conformations. PMID:26709870

  11. Mono- and Dinuclear Macrocyclic Calcium Complexes as Platforms for Mixed-Metal Complexes and Clusters.

    PubMed

    Connolly, Emma A; Leeland, James W; Love, Jason B

    2016-01-19

    Mono- and dinuclear calcium complexes of the Schiff-base macrocycles H4L have been prepared and characterized spectroscopically and crystallographically. In the formation of Ca(THF)2(H2L(1)), Ca2(THF)2(μ-THF)(L(1)), and Ca2(THF)4(L(2)), the ligand framework adopts a bowl-shaped conformation instead of the conventional wedge, Pacman-shaped structure as seen with the anthracenyl-hinged complex Ca2(py)5(L(3)). The mononuclear calcium complex Ca(THF)2(H2L(1)) reacts with various equivalents of LiN(SiMe3)2 to form calcium/alkali metal clusters and dinuclear transition metal complexes when reacted subsequently with transition metal salts. The dinuclear calcium complex Ca2(THF)2(μ-THF)(L(1)), when reacted with various equivalents of NaOH, is shown to act as a platform for the formation of calcium/alkali metal hydroxide clusters, displaying alternate wedged and bowl-shaped conformations.

  12. Luminescence of ortho-metallated platinum(II) complexes

    NASA Astrophysics Data System (ADS)

    Maestri, Mauro; Sandrini, Diana; Balzani, Vincenzo; Chassot, Laurent; Jolliet, Philippe; von Zelewsky, Alex

    1985-12-01

    The absorption spectra, emission spectra, and emission lifetimes of Pt(Phpy) 2, Pt(Thpy) 2, and Pt(Bhq) 2 complexes (Phpy -, Thpy -, and Bhq - are the ortho C-deprotonated forms of 2-phenylpyridine, 2-(2-thienyl)-pyridine, and benzo(h)quinoline) have been studied and compared with those of the C-protonated neutral ligands. For all complexes examined the low-energy absorption bands in the near UV and visible region are assigned to metal-to-ligand charge-transfer transitions. The strong and structured luminescence emissions observed in the 500-600 nm region (lifetime in the microsecond range at 77 K) are assigned to metal-to-ligand charge-transfer excited states.

  13. 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.

  14. 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.

  15. On the charge transfer in the "single-sheet graphene-intercalated metal layer-SiC substrate" system

    NASA Astrophysics Data System (ADS)

    Davydov, S. Yu.

    2014-02-01

    The proposed scheme for the consideration of charge transfer in the three-layer Gr/Me/SiC system (where Gr is a single-sheet graphene, Me is an intercalated metal layer, and SiC is a substrate) contains three stages. At the first stage, a metal monolayer adsorbed on silicon carbide is considered and the charge of adatoms in this monolayer is calculated. At the second stage, the shift of the Dirac point of free-standing single-layer graphene in an electrostatic field induced by charged adatoms of the monolayer is estimated. At the third stage, a weak interaction between Me/SiC and free-standing graphene is included, which allows electrons to tunnel but does not significantly distort the density of states of free-standing graphene. Estimations are performed for n- and p-type 6 H-SiC(0001) substrates and Cu, Ag, and Au layers. The charge state of the graphene sheet and the shift of the Dirac point with respect to the Fermi level of the system are calculated. A comparison with the available experimental and theoretical results shows that the proposed scheme works quite satisfactorily.

  16. 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.

  17. Controlling Magnetism of a Complex Metallic System Using Atomic Individualism

    NASA Astrophysics Data System (ADS)

    Mudryk, Y.; Paudyal, D.; Pecharsky, V. K.; Gschneidner, K. A., Jr.; Misra, S.; Miller, G. J.

    2010-08-01

    When the complexity of a metallic compound reaches a certain level, a specific location in the structure may be critically responsible for a given fundamental property of a material while other locations may not play as much of a role in determining such a property. The first-principles theory has pinpointed a critical location in the framework of a complex intermetallic compound—Gd5Ge4—that resulted in a controlled alteration of the magnetism of this compound using precise chemical tools.

  18. 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.

  19. 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. PMID:25600485

  20. 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.

  1. Trianionic pincer and pincer-type metal complexes and catalysts.

    PubMed

    O'Reilly, Matthew E; Veige, Adam S

    2014-09-01

    Trianionic pincer and pincer-type ligands are the focus of this review. Metal ions from across the periodic table, from main group elements, transition metals, and the rare earths, are combined with trianionic pincer ligands to produce some of the most interesting complexes to appear in the literature over the past decade. This review provides a comprehensive examination of the synthesis, characterization, properties, and catalytic applications of trianionic pincer metal complexes. Some of the interesting applications employing trianionic pincer and pincer-type complexes include: (1) catalyzed aerobic oxidation, (2) alkene isomerization, (3) alkene and alkyne polymerization, (4) nitrene and carbene group transfer, (5) fundamental transformations such as oxygen-atom transfer, (6) nitrogen-atom transfer, (7) O2 activation, (8) C-H bond activation, (9) disulfide reduction, and (10) ligand centered storage of redox equivalents (i.e. redox active ligands). Expansion of the architecture, type of donor atoms, chelate ring size, and steric and electronic properties of trianionic pincer ligands has occurred rapidly over the past ten years. This review is structured according to the type of pincer donor atoms that bind to the metal ion. The type of donor atoms within trianionic pincer and pincer-type ligands to be discussed include: NCN(3-), OCO(3-), CCC(3-), redox active NNN(3-), NNN(3-), redox active ONO(3-), ONO(3-), and SNS(3-). Since this is the first review of trianionic pincer and pincer-type ligands, an emphasis is placed on providing the reader with in-depth discussion of synthetic methods, characterization data, and highlights of these complexes as catalysts. PMID:24927219

  2. Group 9 Metal Complexes of meso-Aryl-Substituted Rubyrin.

    PubMed

    Soya, Takanori; Osuka, Atsuhiro

    2015-07-20

    Invited for the cover of this issue are Takanori Soya and Atsuhiro Osuka at Kyoto University. The image depicts Group 9 metal (Co, Rh, and Ir) complexes of meso-aryl-substituted rubyrin and a meteorite approaching to the atmosphere. A large amount of Iridium is often contained in meteorites. Read the full text of the article at 10.1002/chem.201501080. PMID:26042817

  3. 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.

  4. 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.

  5. 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

  6. Mechanics of metal-catecholate complexes: The roles of coordination state and metal types

    PubMed Central

    Xu, Zhiping

    2013-01-01

    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. PMID:24107799

  7. 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.

  8. A Study on the Welding Characteristics of Tailor Welded Blank Metal Sheets Using GTAW and Laser Welding

    NASA Astrophysics Data System (ADS)

    Thasanaraphan, Pornsak

    In this study, a computational and experimental effort was carried out to qualitatively understand the weld pool shape, distortion and residual stress for continuous laser welding and manual pulsed gas metal arc welding. For all the welding simulations given in this dissertation, a welding specific finite element package, SYSWELD, is used. This research focuses on the welding behavior observed in light-weight metal structures known as the tailor-welded blanks, TWBs. They are a combination of two or more metal sheets with different thickness and/or different materials that are welded together in a single plane prior to forming, e.g., stamping. They made from the low carbon steel. As laser welding experiment results show, the weld pool shape at the top and bottom surface, is strongly influenced by surface tension, giving it a characteristic hourglass shape. In order to simulate the hourglass shape, a new volumetric heat source model was developed to predict the transient temperature profile and weld pool shape, including the effect of surface tension. Tailor welded blanks with different thicknesses were examined in the laser welding process. All major physical phenomena such as thermal conduction, heat radiation and convection heat losses are taken into account in the model development as well as temperature-dependant thermal and mechanical material properties. The model is validated for the case of butt joint welding of cold rolled steel sheets. The results of the numerical simulations provide temperature distributions representing the shape of the molten pool, distortion and residual stress with varying laser beam power and welding speed. It is demonstrated that the finite element simulation results are in good agreement with the experiment results. This includes the weld pool shape and sheet metal distortion. While there is no experimental data to compare directly with residual stress results, the distorted shape provides an indirect measure of the welding

  9. Redox noninnocence of nitrosoarene ligands in transition metal complexes.

    PubMed

    Tomson, Neil C; Labios, Liezel A; Weyhermüller, Thomas; Figueroa, Joshua S; Wieghardt, Karl

    2011-06-20

    Studies on the coordination of nitrosoarene (ArNO) ligands to late-transition metals are used to provide the first definition of the geometric, spectroscopic, and computational parameters associated with a PhNO electron-transfer series. Experimentally, the Pd complexes PdCl(2)(PhNO)(2), PdL(2)(PhNO)(2), and PdL(2)(TolNO) (L = CNAr(Dipp2); Ar(Dipp2) = 2,6-(2,6-(i)Pr(2)C(6)H(3))(2)-C(6)H(3)) are characterized as containing (PhNO)(0), (PhNO)(•1-), and (TolNO)(2-) ligands, respectively, and the structural and spectroscopic changes associated with this electron transfer series provide the basis for an extensive computational study of these and related ArNO-containing late-transition metal complexes. Most notable from the results is the unambiguous characterization of the ground state electronic structure of PdL(2)(PhNO)(2), found to be the first isolable, transition metal ion complex containing an η(1)-N-bound π-nitrosoarene radical anion. In addition to the electron transfer series, the synthesis and characterization of the Fe complex [Fe(TIM)(NCCH(3))(PhNO)][(PF(6))(2)] (TIM = 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene) allows for comparison of the geometric and spectroscopic features associated with metal-to-ligand π-backbonding as opposed to (PhNO)(•1-) formation. Throughout these series of complexes, the N-O, M-N, and C-N bond distances as well as the N-O stretching frequencies and the planarity of the ArNO ligands provided distinct parameters for each ligand oxidation state. Together, these data provide a delineation of the factors needed for evaluating the oxidation state of nitrosoarene ligands bound to transition metals in varying coordination modes.

  10. 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.

  11. Systematic investigation of geometrical parameters’ influence on the appearance of surface deflections in sheet metal forming

    NASA Astrophysics Data System (ADS)

    Weinschenk, A.; Volk, W.

    2016-08-01

    Surface deflections occur during springback, which follows deep drawing. They highly affect the visual appearance of outer skin components and are, therefore, undesirable. In this work, the influence of the part geometry on the shaping of surface deflections is investigated. The geometrical parameters of an exemplary component are varied and existing surface deflections are detected. For this, a component consisting of a multiple curved surface with an inserted door handle hollow is used, and AA6016, with a sheet thickness of 1.0 mm, as well as DC06, with a sheet thickness of 0.7 mm, are chosen. After the simulations are performed in AutoForm plus R6 TM , a virtual stone, Three-Point Gauging and the analysis of curvatures of the part before and after springback are used to detect surface deflections.

  12. Protection of Metal Artifacts with the Formation of Metal-Oxalates Complexes by Beauveria bassiana.

    PubMed

    Joseph, Edith; Cario, Sylvie; Simon, Anaële; Wörle, Marie; Mazzeo, Rocco; Junier, Pilar; Job, Daniel

    2011-01-01

    Several fungi present high tolerance to toxic metals and some are able to transform metals into metal-oxalate complexes. In this study, the ability of Beauveria bassiana to produce copper oxalates was evaluated. Growth performance was tested on various copper-containing media. B. bassiana proved highly resistant to copper, tolerating concentrations of up to 20 g L(-1), and precipitating copper oxalates on all media tested. Chromatographic analyses showed that this species produced oxalic acid as sole metal chelator. The production of metal-oxalates can be used in the restoration and conservation of archeological and modern metal artifacts. The production of copper oxalates was confirmed directly using metallic pieces (both archeological and modern). The conversion of corrosion products into copper oxalates was demonstrated as well. In order to assess whether the capability of B. bassiana to produce metal-oxalates could be applied to other metals, iron and silver were tested as well. Iron appears to be directly sequestered in the wall of the fungal hyphae forming oxalates. However, the formation of a homogeneous layer on the object is not yet optimal. On silver, a co-precipitation of copper and silver oxalates occurred. As this greenish patina would not be acceptable on silver objects, silver reduction was explored as a tarnishing remediation. First experiments showed the transformation of silver nitrate into nanoparticles of elemental silver by an unknown extracellular mechanism. The production of copper oxalates is immediately applicable for the conservation of copper-based artifacts. For iron and silver this is not yet the case. However, the vast ability of B. bassiana to transform toxic metals using different immobilization mechanisms seems to offer considerable possibilities for industrial applications, such as the bioremediation of contaminated soils or the green synthesis of chemicals. PMID:22291684

  13. 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.

  14. 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.

  15. Metal-dithiocarbamate complexes: chemistry and biological activity.

    PubMed

    Hogarth, Graeme

    2012-10-01

    Dithiocarbamates are highly versatile mono-anionic chelating ligands which form stable complexes with all the transition elements and also the majority of main group, lanthanide and actinide elements. They are easily prepared from primary or secondary amines and depending upon the nature of the cation can show good solubility in water or organic solvents. They are related to the thiuram disulfides by a one-electron redox process (followed by dimerisation via sulfur-sulfur bond formation) which is easily carried out upon addition of iodide or ferric salts. Dithiocarbamates are lipophilic and generally bind to metals in a symmetrical chelate fashion but examples of other coordination modes are known, the monodentate and anisobidentate modes being most prevalent. They are planar sterically non-demanding ligands which can be electronically tuned by judicious choice of substituents. They stabilize metals in a wide range of oxidation states, this being attributed to the existence of soft dithiocarbamate and hard thioureide resonance forms, the latter formally resulting from delocalization of the nitrogen lone pair onto the sulfurs, and consequently their complexes tend to have a rich electrochemistry. Tetraethyl thiuramdisulfide (disulfiram or antabuse) has been used as a drug since the 1950s but it is only recently that dithiocarbamate complexes have been explored within the medicinal domain. Over the past two decades anti-cancer activity has been noted for gold and copper complexes, technetium and copper complexes have been used in PET-imaging, dithiocarbamates have been used to treat acute cadmium poisoning and copper complexes also have been investigated as SOD inhibitors.

  16. Metal-dithiocarbamate complexes: chemistry and biological activity.

    PubMed

    Hogarth, Graeme

    2012-10-01

    Dithiocarbamates are highly versatile mono-anionic chelating ligands which form stable complexes with all the transition elements and also the majority of main group, lanthanide and actinide elements. They are easily prepared from primary or secondary amines and depending upon the nature of the cation can show good solubility in water or organic solvents. They are related to the thiuram disulfides by a one-electron redox process (followed by dimerisation via sulfur-sulfur bond formation) which is easily carried out upon addition of iodide or ferric salts. Dithiocarbamates are lipophilic and generally bind to metals in a symmetrical chelate fashion but examples of other coordination modes are known, the monodentate and anisobidentate modes being most prevalent. They are planar sterically non-demanding ligands which can be electronically tuned by judicious choice of substituents. They stabilize metals in a wide range of oxidation states, this being attributed to the existence of soft dithiocarbamate and hard thioureide resonance forms, the latter formally resulting from delocalization of the nitrogen lone pair onto the sulfurs, and consequently their complexes tend to have a rich electrochemistry. Tetraethyl thiuramdisulfide (disulfiram or antabuse) has been used as a drug since the 1950s but it is only recently that dithiocarbamate complexes have been explored within the medicinal domain. Over the past two decades anti-cancer activity has been noted for gold and copper complexes, technetium and copper complexes have been used in PET-imaging, dithiocarbamates have been used to treat acute cadmium poisoning and copper complexes also have been investigated as SOD inhibitors. PMID:22931592

  17. Preparation of molecule-based magnets from metal thiocyanate complexes

    NASA Astrophysics Data System (ADS)

    Shurdha, Endrit

    2011-07-01

    The study of magnetism has enabled many technological applications that are ubiquitous in our daily life. Presently, most of the magnetic applications use metal/metal oxide magnets, which are readily available. In the last few decades, research has focused on a new class of magnetic materials, molecule-based magnets. This class of materials has diverse physical and chemical properties, which can be controlled by synthetic methods. Utilizing a variety of metals and ligands, researchers can control and fine tune various aspects of these magnetic materials, such as structural connections and possibly magnetic properties. Tetracyanoethylene (TCNE) is widely used in the preparation of molecule-based magnets due to its unique electronic and connectivity properties. TCNE has multiple binding sites, which gives it a diverse range of structural connectivity. Also, TCNE can be reduced easily to form a radical anion, which facilitates spin communication between metal centers allowing isolation of magnetically ordered systems such as V(TCNE)2 (a room temperature molecule-based magnet). M-TCNE magnets are prepared from solvated MII complexes or a metal carbonyl and TCNE in dichloromethane. The reaction involves the oxidation of the MII to MIII and the reduction of TCNE. More coordinating solvents used to prepare TCNE molecule-based magnets facilitate the dimerization of the radical TCNE, which does not allow for long-range ordering. The work presented herein will show the synthesis of MII thiocyanate complexes and their reaction with TCNE radical anion to yield M(TCNE)[C4(CN)8]1/2, which is obtained through ligand substitution between TCNE and thiocyanate. The development of new MII thiocyanate complexes through MII(NCMe)x(BF4)2 (x = 4, 6) in acetone, acetonitrile, and tetrahydrofuran will be the focus of Chapter 2. Also, in Chapter 2, structural and magnetic characterization will be discussed. Few of the metal thiocyanate complexes exhibit antiferromagnetic ordering at

  18. 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

  19. Ag-DNA Emitter: Metal Nanorod or Supramolecular Complex?

    PubMed

    Ramazanov, Ruslan R; Sych, Tomash S; Reveguk, Zakhar V; Maksimov, Dmitriy A; Vdovichev, Artem A; Kononov, Alexei I

    2016-09-15

    Ligand-stabilized luminescent metal clusters, in particular, DNA-based Ag clusters, are now employed in a host of applications such as sensing and bioimaging. Despite their utility, the nature of their excited states as well as detailed structures of the luminescent metal-ligand complexes remain poorly understood. We apply a new joint experimental and theoretical approach based on QM/MM-MD simulations of the fluorescence excitation spectra for three Ag clusters synthesized on a 12-mer DNA. Contrary to a previously proposed "rod-like" model, our results show that (1) three to four Ag atoms suffice to form a partially oxidized nanocluster emitting in visible range; (2) charge transfer from Ag cluster to DNA contributes to the excited states of the complexes; and (3) excitation spectra of the clusters are strongly affected by the bonding of Ag atoms to DNA bases. The presented approach can also provide a practical way to determine the structure and properties of other luminescent metal clusters. PMID:27564452

  20. 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.

  1. 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...

  2. 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...

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

    PubMed

    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. PMID:27384871

  4. 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.

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

    PubMed

    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.

  6. 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.

  7. Identification of metal species by ESI-MS/MS through release of free metals from the corresponding metal-ligand complexes.

    PubMed

    Tsednee, Munkhtsetseg; Huang, Yu-Chen; Chen, Yet-Ran; Yeh, Kuo-Chen

    2016-05-31

    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.

  8. Spontaneous symmetry breaking and strong deformations in metal adsorbed graphene sheets

    NASA Astrophysics Data System (ADS)

    Jalbout, A. F.; Ortiz, Y. P.; Seligman, T. H.

    2013-03-01

    We study the adsorption of Li to graphene flakes simulated as aromatic molecules. Surprisingly the out of plane deformation is much stronger for the double adsorption from both sides to the same ring than for a single adsorption, although a symmetric solution seems possible. We thus have an interesting case of spontaneous symmetry breaking. While we cannot rule out a Jahn Teller deformation with certainty, this explanation seems unlikely and other options are discussed. We find a similar behavior for boron-nitrogen sheets, and also for other light alkalines as adsorbants.

  9. Springback control in sheet metal bending by laser-assisted bending: Experimental analysis, empirical and neural network modelling

    NASA Astrophysics Data System (ADS)

    Gisario, A.; Barletta, M.; Conti, C.; Guarino, S.

    2011-12-01

    The present investigation deals with the control of springback phenomena in the bending process of aluminium sheets by hybrid forming process. Metal substrates were pre-bent to nominal shapes on a built-ad-hoc mould after being constrained on it. Then, they were post-treated by high power diode laser to prevent the deformation of the pre-bent sheets after the release of the constraints. The extent of springback phenomena were estimated by measuring the difference between the nominal bending angles and those achieved on the unconstrained substrates after laser post-treatments. Analytical models, aimed at predicting the springback by varying the setting of the operational parameters of the forming process, were developed. Neural network solutions were also proposed to improve the matching between experimental and numerical data, with the Multi-Layer Perceptrons trained by Back-Propagation algorithm being the fittest one. On this basis, a control modulus very useful to practitioners for automation and simulation purposes was built-on.

  10. 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

  11. 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.

  12. Applications of DFT to Lanthanides and Precious Metal Complexes

    NASA Astrophysics Data System (ADS)

    Balboa, Alex; Hurley, Margaret; Jenkins, Amanda; None Collaboration; None Collaboration

    2014-03-01

    Density functional theory is widely used for computational characterization of novel materials. While study of materials containing the lighter elements is commonplace, the application of these methods to the bottom of the periodic table, including the lanthanides and the heavier precious metals such as Osmium, requires careful validation. Here we present results of recent quantum mechanical studies to characterize Lanthanide/Graphene Materials and assess the suitability of DFT for these systems. Additionally, we will present recent work on similar application of DFT to characterize Os bipridine complexes.

  13. Springback Analysis in Sheet Metal Forming of Non-linear Work-Hardening material Under Pure Bending

    NASA Astrophysics Data System (ADS)

    Lal, Radha Krishna; Dwivedi, Jai Prakash; Bhagat, Manish Kumar; Singh, Virendra Pratap

    2016-09-01

    This paper deals with the springback analysis in sheet metal forming for non-linear work-hardening material under pure bending. Using the deformation theory of plasticity, formulation of the problem and spring back ratio is derived using Ramberg-Osgood stress strain relationship with Tresca and Von-Mises yielding criteria. The results have been representing the effect of different value of Y/E or σo/E ratio, different values of strain hardening index (n), Poisson's ratio (ν) and thickness on springback ratio (R0/Rf). The main aim of this paper is to study the effects of the thickness, Y/E ratio, n and Poisson's ratio in spring back ratio.

  14. A Straightforward Electrochemical Approach to Imine- and Amine-bisphenolate Metal Complexes with Facile Control Over Metal Oxidation State.

    PubMed

    Chapman, Michael R; Henkelis, Susan E; Kapur, Nikil; Nguyen, Bao N; Willans, Charlotte E

    2016-08-01

    Synthetic methods to prepare organometallic and coordination compounds such as Schiff-base complexes are diverse, with the route chosen being dependent upon many factors such as metal-ligand combination and metal oxidation state. In this work we have shown that electrochemical methodology can be employed to synthesize a variety of metal-salen/salan complexes which comprise diverse metal-ligand combinations and oxidation states. Broad application has been demonstrated through the preparation of 34 complexes under mild and ambient conditions. Unprecedented control over metal oxidation state (M(II/III/IV) where M=Fe, Mn) is presented by simple modification of reaction conditions. Along this route, a general protocol-switch is described which allows access to analytically pure Fe(II/III)-salen complexes. Tuning electrochemical potential, selective metalation of a Mn/Ni alloy is also presented which exclusively delivers Mn(II/IV)-salen complexes in high yield. PMID:27547645

  15. Fluoroquinolone-metal complexes: a route to counteract bacterial resistance?

    PubMed

    Feio, Maria J; Sousa, Isabel; Ferreira, Mariana; Cunha-Silva, Luís; Saraiva, Raúl G; Queirós, Carla; Alexandre, José G; Claro, Vasco; Mendes, Adélia; Ortiz, Rosa; Lopes, Sandra; Amaral, Ana Luísa; Lino, João; Fernandes, Patrícia; Silva, Ana João; Moutinho, Lisete; de Castro, Baltazar; Pereira, Eulália; Perelló, Lourdes; Gameiro, Paula

    2014-09-01

    Microbial resistance to antibiotics is one of the biggest public health threats of the modern world. Antibiotic resistance is an area of much clinical relevance and therefore research that has the potential to identify agents that may circumvent it or treat resistant infections is paramount. Solution behavior of various fluoroquinolone (FQ) complexes with copper(II) in the presence and absence of 1,10-phenanthroline (phen) was studied in aqueous solution, by potentiometry and/or spectrophotometry, and are herein described. The results obtained showed that under physiological conditions (micromolar concentration range and pH7.4) only copper(II):FQ:phen ternary complexes are stable. Hence, these complexes were synthesised and characterised by means of UV-visible and IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. In these complexes, the FQ acts as a bidentate ligand that coordinates the metal cation through the carbonyl and carboxyl oxygen atoms and phen coordinates through two N-atoms forming the equatorial plane of a distorted square-pyramidal geometry. The fifth position of the penta-coordinated Cu(II) centre is generally occupied axially by an oxygen atom from a water molecule or from a nitrate ion. Minimum inhibitory concentration (MIC) determinations of the complexes and comparison with free FQ in various E. coli strains indicate that the Cu-complexes are as efficient antimicrobials as the free antibiotic. Moreover, results strongly suggest that the cell intake route of both species is different supporting, therefore, the complexes' suitability as candidates for further biological testing in FQ-resistant microorganisms.

  16. Numerical biaxial tensile test for sheet metal forming simulation of aluminium alloy sheets based on the homogenized crystal plasticity finite element method

    NASA Astrophysics Data System (ADS)

    Yamanaka, A.; Ishii, Y.; Hakoyama, T.; Eyckens, P.; Kuwabara, T.

    2016-08-01

    The simulation of the stretch forming of A5182-O aluminum alloy sheet with a spherical punch is performed using the crystal plasticity (CP) finite element method based on the mathematical homogenization theory. In the simulation, the CP constitutive equations and their parameters calibrated by the numerical and experimental biaxial tensile tests with a cruciform specimen are used. The results demonstrate that the variation of the sheet thickness distribution simulated show a relatively good agreement with the experimental results.

  17. Metal Complexes of meso-meso Linked Corrole Dimers.

    PubMed

    Ooi, Shota; Tanaka, Takayuki; Osuka, Atsuhiro

    2016-09-01

    Cobalt, gallium, silver, and copper complexes of 5,5'-linked corrole dimer 1 and 10,10'-linked corrole dimer 2 were synthesized by metalations with Co(OAc)2·4H2O, GaCl3, AgOAc, and Cu(OAc)2·H2O, respectively, in good yields. The structures of cobalt(III), gallium(III), and silver(III) complexes have been unambiguously revealed by X-ray diffraction analysis. Their optical and electrochemical properties have been studied, which revealed different electronic interactions between the two corrole units depending upon the positions of meso-meso linkage and axial-ligand coordination modes. PMID:27533780

  18. Photophysical investigation of palladium(II) ortho-metalated complexes

    SciTech Connect

    Craig, C.A.; Watts, R.J. )

    1989-01-25

    Syntheses and structural characterizations of four complexes of Pd(II) with ortho-metalated 2-phenylpyridinate (ppy{sup minus}) are reported. These complexes include a parent dimer, (Pd(ppy)Cl){sub 2}, and three derivative monomers, (Pd(ppy)(bpy))Cl, (Pd(ppy)(en))Cl, and (Pd(ppy)(CO)Cl), whereby = 2,2'-bipyridine and en = ethylenediamine. Photophysical characterizations of these species indicate low-energy absorption bands ({approximately}360 nm) and emission bands at 77 K ({approximately}460 nm) that are assigned to transitions located on the ppy{sup {minus}} ligand. Some evidence for low-energy charge-transfer states is found in trends in luminescence lifetimes. 2 tabs., 5 figs., 21 refs.

  19. 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.

  20. Synthesis of Metal Oxide Particles Using Reaction Route from Rare-Earth Metal-EDTA Complexes

    NASA Astrophysics Data System (ADS)

    Komatsu, Keiji; Tsuchiya, Takaaki; Hasebe, Yasuhiro; Sekiya, Tetsuo; Toyama, Ayumu; Nakamura, Atsushi; Akasaka, Hiroki; Saitoh, Hidetoshi

    2014-06-01

    Highly dense, spherical yttria (Y2O3) and erbia (Er2O3) particles were synthesized from their corresponding metal-ethylenediaminetetraacetic (EDTA) complexes. The EDTA·Y·H and EDTA·Er·H complexes were prepared in powdered form. These complexes were used as the staring materials for synthesis of the Y2O3 and Er2O3 particles. The particles were synthesized using an H2-O2 flame produced with a commercial flame spray apparatus. Crystalline structure, surface and cross-sectional morphologies, and elemental distribution of the synthesized particles were investigated. It was confirmed that the crystalline phases of the Y2O3 and Er2O3 particles were homogeneous. In addition, the elemental distribution of the particles was uniform. These results indicate that dense, spherical particles of Y2O3 and Er2O3 have been synthesized with EDTA·Y·H and EDTA·Er·H complexes, respectively.

  1. 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.

  2. 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

  3. Transistor-like behavior of transition metal complexes.

    PubMed

    Albrecht, Tim; Guckian, Adrian; Ulstrup, Jens; Vos, Johannes G

    2005-07-01

    Electron transport through semiconductor and metallic nanoscale structures, molecular monolayers, and single molecules connected to external electrodes display rectification, switch, and staircase functionality of potential importance in future miniaturization of electronic devices. Common to most reported systems is, however, ultrahigh vacuum and/or cryogenic working conditions. Here we introduce a single-molecule device concept based on a class of robust redox active transition metal (Os(II)/(III)) complexes inserted between the working electrode and tip in an electrochemical scanning tunneling microscope (in situ STM). This configuration resembles a single-molecule transistor, where the reference electrode corresponds to the gate electrode. It operates at room temperature in a condensed matter (here aqueous) environment. Amplification on-off ratios up to 50 are found when the redox level is brought into the energy window between the Fermi levels of the electrodes by the overpotential ("gate voltage"). The current-voltage characteristics for two Os(II)/(III) complexes have been characterized systematically and supported by theoretical frames based on molecular charge transport theory.

  4. Synchrotron ultrafast techniques for photoactive transition metal complexes.

    PubMed

    Borfecchia, Elisa; Garino, Claudio; Salassa, Luca; Lamberti, Carlo

    2013-07-28

    In the last decade, the use of time-resolved X-ray techniques has revealed the structure of light-generated transient species for a wide range of samples, from small organic molecules to proteins. Time resolutions of the order of 100 ps are typically reached, allowing one to monitor thermally equilibrated excited states and capture their structure as a function of time. This review aims at providing a general overview of the application of time-resolved X-ray solution scattering (TR-XSS) and time-resolved X-ray absorption spectroscopy (TR-XAS), the two techniques prevalently employed in the investigation of light-triggered structural changes of transition metal complexes. In particular, we herein describe the fundamental physical principles for static XSS and XAS and illustrate the theory of time-resolved XSS and XAS together with data acquisition and analysis strategies. Selected pioneering examples of photoactive transition metal complexes studied by TR-XSS and TR-XAS are discussed in depth.

  5. Manganese Complexes of 1,3,5-triaza-7-phosphaadamantane (PTA): The First Nitrogen Bound Transition Metal Complex of PTA

    SciTech Connect

    Frost,B.; Bautista, C.; Huang, R.; Shearer, J.

    2006-01-01

    The structures of two manganese(II) complexes of 1,3,5-triaza-7-phosphaadamantane (PTA) reveal the first transition-metal complexes of PTA in which the metal preferentially coordinates to a nitrogen and not the phosphorus of PTA. The coordination environment about the manganese was probed using X-ray crystallography (solid state) and EXAFS spectroscopy (solution).

  6. Biodegradable polymer-metal complexes for gene and drug delivery.

    PubMed

    Hosseinkhani, Hossein; Hosseinkhani, Mohsen

    2009-01-01

    The delivery of genes and drugs into cells has increasingly attracted attention for the generation of genetically engineered cells. Successful drug delivery will have enormous academic, clinical, and practical impacts on gene therapy, cell and molecular biology, pharmaceutical and food industries, and bio-production. The major aim of gene therapy is to deliver genetic materials into cells effectively, genetically modifying and repairing cell functions with the possibility of inducing therapeutic healing of disease. The genetic material includes DNA, RNA, antisense, decoy DNA, and ribozymes. The aim is that the appropriate transfection would allow diseased cells to return to a healthy condition. The genetic manipulation is often manifested in the mechanisms of intracellular actions of genes and proteins, and may play an important role in making clear the key genes associated with various diseases. Based on fundamental and scientific knowledge, the delivery technology of genetic material should be applicable to producing various proteins of pharmaceutical value (e.g. cytokines, growth factors, and antibodies) and also to producing seeds resistant to harmful insects and cold weather damage. This implies that the cells might be enhanced to produce valuable pharmaceutical and food products. For each approach, it is important, for successful gene expression, to select an appropriate gene to be delivered as well as to develop the gene delivery technology to enhance transfection efficiency. This review will provide an overview of the enhanced gene expression of plasmid DNA complexed with new non-viral gene delivery vehicles by biodegradable biopolymer-metal complex, introducing our recent research data to emphasize the technical feasibility of biopolymer-metal complexes in gene therapy and biotechnology.

  7. 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.

  8. 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.

  9. 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…

  10. Targeting divalent metal cations with Re(I) tetrazolato complexes.

    PubMed

    Fiorini, Valentina; Ranieri, Anna Maria; Muzzioli, Sara; Magee, Karen D M; Zacchini, Stefano; Akabar, Nurshadrina; Stefan, Alessandra; Ogden, Mark I; Massi, Massimiliano; Stagni, Stefano

    2015-12-21

    In order to exploit their potential as versatile luminescent sensors, four new Re(I)-tetrazolato complexes with the general formula fac-[Re(CO)3(diim)(L)], where diim is 2,2'-bipyridine (bipy) or 1,10-phenanthroline (phen) and L(-) is either the anion 5-(2'-pyridyl)tetrazolato (2-PTZ(-)) or 5-(2'-quinolyl)tetrazolato (2-QTZ(-)), were prepared and fully characterized. In all cases, the regioselective coordination of the Re(I) center through the N2 atom of the tetrazolato ring was observed. This particular feature ensures the availability of the diiminic (N^N) site that was systematically incorporated into the structure of the 2-PTZ(-) and 2-QTZ(-) ligands for further coordination with metal cations. Such a diimine-type coordination mode was preliminarily tested by using the mononuclear Re(I) complexes as N^N ligands for the preparation of two [(N^N)Cu(POP)] cationic species, where POP is the chelating diphosphine bis[2-(diphenylphosphino)phenyl]ether. The X-ray structures of the resulting Re(I)-Cu(I) dyads revealed that the Re(I) mononuclear complexes effectively behaved as chelating N^N ligands with respect to the [Cu(POP)](+) fragment, the coordination of which also resulted in significant modification of the Re(I)-centered luminescence. With these data in hand, the luminescent sensing abilities of the four new Re(I) tetrazolato complexes were screened with respect to divalent metal ions of toxicological and biological importance such as Zn(II), Cd(II) and Cu(II). The interaction of the Re(I) complexes with Zn(II) and Cd(II) was witnessed by the evident blue shift (Δλmax = 22-36 nm) of the emission maxima, which was also accompanied by a significant elongation of the emission lifetimes. On the contrary, the addition of the cupric ion caused substantial quenching of the radiative processes originating from the Re(I) luminophores. PMID:26554352

  11. Multi-dimensional transition-metal coordination polymers of 4,4'-bipyridine-N,N'-dioxide: 1D chains and 2D sheets.

    PubMed

    Jia, Junhua; Blake, Alexander J; Champness, Neil R; Hubberstey, Peter; Wilson, Claire; Schröder, Martin

    2008-10-01

    Reaction of 4,4'-bipyridine -N, N' -dioxide (L) with a variety of transition-metal salts in MeOH affords a range of coordination polymer products. For the complexes [FeCl 3(mu-L)] infinity, 1, and ([Cu(L) 2(OHMe) 2(mu-L)].2PF 6. n(solv)) infinity, 2, 1D chain structures are observed, whereas ([Mn(mu-L) 3].2ClO 4) infinity, 3, and ([Cu(mu-L) 3].2BF 4) infinity, 4, both show 2D sheet architectures incorporating an unusual 3 (6)- hxl topology. The more common 4 (4)- sql topology is observed in [Cd(ONO 2) 2(mu-L) 2] infinity, 5, ([Cu(OHMe) 2(mu-L) 2].2ZrF 5) infinity, 6, ([Cu(L) 2(mu-L) 2].2EF 6) infinity ( 7 E = P; 8 E = Sb), and ([Et 4N][Cu(OHMe) 0.5(mu-L) 2(mu-FSiF 4F) 0.5].2SbF 6. n(solv)) infinity, 9. In 6, the [ZrF 5] (-) anion, formed in situ from [ZrF 6] (2-), forms 1D anionic chains ([ZrF 5] (-)) infinity of vertex-linked octahedra, and these chains thread through a pair of inclined polycatenated ([Cu(OHMe) 2(mu-L) 2] (2+)) infinity 4 (4)- sql grids to give a rare example of a triply intertwined coordination polymer. 9 also shows a 3D matrix structure with 4 (4)- sql sheets of stoichiometry ([Cu(L) 2] (2+)) infinity coordinatively linked by bridging [SiF 6] (2-) anions to give a structure of 5-c 4 (4).6 (6)- sqp topology. The mononuclear [Cu(L) 6].2BF 4 ( 10) and [Cd(L) 6].2NO 3 ( 11) and binuclear complexes [(Cu(L)(OH 2)) 2(mu-L) 2)].2SiF 6. n(solv), 12, are also reported. The majority of the coordination polymers are free of solvent and are nonporous. Thermal treatment of materials that do contain solvent results in structural disintegration of the complex structures giving no permanent porosity.

  12. 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.

  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. Excited-state properties of a triply ortho-metalated iridium(III) complex

    SciTech Connect

    King, K.A.; Spellane, P.J.; Watts, R.J.

    1985-03-06

    The characterization of the ground and luminescent excited states of a triply ortho-metalated complex of ppy, fac-Ir(ppy)/sub 3/ (ppy = 2-phenylpyridine) is effected. This complex, which is the first triply ortho-metalated ppy species to be characterized, is one of the strongest transition-metal photoreductants thus far reported. 20 references, 2 figures.

  15. A novel mode of DNA recognition by a beta-sheet revealed by the solution structure of the GCC-box binding domain in complex with DNA.

    PubMed Central

    Allen, M D; Yamasaki, K; Ohme-Takagi, M; Tateno, M; Suzuki, M

    1998-01-01

    The 3D solution structure of the GCC-box binding domain of a protein from Arabidopsis thaliana in complex with its target DNA fragment has been determined by heteronuclear multidimensional NMR in combination with simulated annealing and restrained molecular dynamic calculation. The domain consists of a three-stranded anti-parallel beta-sheet and an alpha-helix packed approximately parallel to the beta-sheet. Arginine and tryptophan residues in the beta-sheet are identified to contact eight of the nine consecutive base pairs in the major groove, and at the same time bind to the sugar phosphate backbones. The target DNA bends slightly at the central CG step, thereby allowing the DNA to follow the curvature of the beta-sheet. PMID:9736626

  16. 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.

  17. 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.

  18. A DFT investigation of CO adsorption on VIIIB transition metal-doped graphene sheets

    NASA Astrophysics Data System (ADS)

    Wanno, Banchob; Tabtimsai, Chanukorn

    2014-03-01

    Adsorptions of CO on pristine, Fe-, Ru-, Os-, Co-, Rh-, Ir-, Ni-, Pd-, and Pt-doped graphene were investigated, using density functional theory calculation at B3LYP/LanL2DZ theoretical level. This work revealed that the transition metal doped graphenes were more highly sensitive to CO adsorption than that of pristine graphene. The Os- and Fe-doped graphenes displayed the strongest interaction with C and O atoms of CO molecule, respectively.

  19. A Study on Flexural Properties of Sandwich Structures with Fiber/Metal Laminate Face Sheets

    NASA Astrophysics Data System (ADS)

    Dariushi, S.; Sadighi, M.

    2013-10-01

    In this work, a new family of sandwich structures with fiber metal laminate (FML) faces is investigated. FMLs have benefits over both metal and fiber reinforced composites. To investigate the bending properties of sandwich beams with FML faces and compare with similar sandwich beams with fibrous composite faces, 6 groups of specimen with different layer arrangements were made and tested. Results show that FML faces have good resistance against transverse local loads and minimize stress concentration and local deformations of skin and core under the loading tip. In addition, FML faces have a good integrity even after plateau region of foam cores and prevent from catastrophic failures, which cannot be seen in fibrous composite faces. Also, FML faces are lighter than metal faces and have better connection with foam cores. Sandwich beams with FML faces have a larger elastic region because of simultaneous deformation of top and bottom faces and larger failure strain thanks to good durability of FMLs. A geometrical nonlinear classical theory is used to predict force-deflection behavior. In this model an explicit formula between symmetrical sandwich beams deflections and applied force which can be useful for designers, is derived. Good agreement is obtained between the analytical predictions and experimental results. Also, analytical results are compared with small deformation solution in a parametric study, and the effects of geometric parameters on difference between linear and nonlinear results are discussed.

  20. Stability of complex coacervate core micelles containing metal coordination polymer.

    PubMed

    Yan, Yun; de Keizer, Arie; Cohen Stuart, Martien A; Drechsler, Markus; Besseling, Nicolaas A M

    2008-09-01

    We report on the stability of complex coacervate core micelles, i.e., C3Ms (or PIC, BIC micelles), containing metal coordination polymers. In aqueous solutions these micelles are formed between charged-neutral diblock copolymers and oppositely charged coordination polymers formed from metal ions and bisligand molecules. The influence of added salt, polymer concentration, and charge composition was investigated by using light scattering and cryo-TEM techniques. The scattering intensity decreases strongly with increasing salt concentration until a critical salt concentration beyond which no micelles exist. The critical micelle concentration increases almost exponentially with the salt concentration. From the scattering results it follows that the aggregation number decreases with the square root of the salt concentration, but the hydrodynamic radius remains constant or increases slightly. It was concluded that the density of the core decreases with increasing ionic strength. This is in agreement with theoretical predictions and is also confirmed by cryo-TEM measurements. A complete composition diagram was constructed based on the composition boundaries obtained from light scattering titrations.

  1. Sorption of heavy metal metatartrate complexes on polystyrene anion exchangers.

    PubMed

    Hubicki, Zbigniew; Geca, Marzena; Kołodyńska, Dorota

    2011-04-01

    The performance of polystyrene anion exchangers in purifying wastewaters containing metatartaric acid and heavy metal ions (especially those from electroless plating processes) was investigated. The following anion exchangers were selected: Lewatit MonoPlus M 500, Lewatit MonoPlus MP 64, Lewatit MP 62 and Amberlite IRA 402. A batch method was used to study the influence of: phase contact time (1-120 min); solution pH (2-9); concentration of initial heavy metal Cu(II), Zn(II), Co(II) and Ni(II) complexes (1.25 x 10(-4) M to 8.0 x 10(-3) M); temperature (303-333K); and interfering ions (Cl-, NO3-, SO4(2-), Ca2+, Mg2+). The amounts of Cu(II), Zn(II), Co(II) and Ni(II) complexes with metatartaric acid sorbed at equilibrium using the strongly basic anion exchanger Lewatit MonoPlus M 500 were equal to 7.25 mg/g, 3.21 mg/g, 3.78 mg/g and 3.98 mg/g, respectively. The equilibrium sorption capacity increased slightly with increasing temperature. The optimal pH sorption was found to be 6.5. The experimental data were analysed using the Langmuir and Freundlich models. The maximum adsorption capacities q(0) determined from the Langmuir adsorption equation equal to 7.53 mg/g, 3.75 mg/g, 3.55 mg/g and 4.60 mg/g were in good agreement with the experimental values for Lewatit MonoPlus M 500. The kinetic data obtained at different concentrations were modelled using pseudo first order, pseudo second order and intraparticle diffusion equations. The experimental data were well described by the pseudo second order kinetic model.

  2. 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.

  3. 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

  4. 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)

  5. 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

  6. 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

  7. 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.

  8. Multi-level modeling for sensitivity assessment of springback in sheet metal forming

    NASA Astrophysics Data System (ADS)

    Lebon, J.; Lequilliec, G.; Coelho, R. Filomeno; Breitkopf, P.; Villon, P.

    2013-05-01

    In this work, we highlight that sensitivity analysis of metal forming process requires both high precision and low cost numerical models. We propose a two-pronged methodology to address these challenges. The deep drawing simulation process is performed using an original low cost semi-analytical approach based on a bending under tension model (B-U-T) with a good accuracy for small random perturbations of the physical and process parameters. The springback sensitivity analysis is based on the Sobol indices approach and performed using an non intrusive efficient methodology based on the post-treatment of the polynomial chaos coefficients.

  9. Search for giant magnetic anisotropy in transition-metal dimers on defected hexagonal boron nitride sheet.

    PubMed

    Li, J; Wang, H; Hu, J; Wu, R Q

    2016-05-28

    Structural and magnetic properties of many transition-metal dimers embedded in a defected hexagonal boron nitride monolayer are investigated through density functional calculations to search for systems with magnetic anisotropy energies (MAEs) larger than 30meV. In particular, Ir-Ir@Dh-BN is found to have both large MAE (∼126 meV) and high structural stability against dissociation and diffusion, and it hence can serve as magnetic unit in spintronics and quantum computing devices. This giant MAE mainly results from the spin orbit coupling and the magnetization of the upper Ir atom, which is in a rather isolated environment. PMID:27250322

  10. Search for giant magnetic anisotropy in transition-metal dimers on defected hexagonal boron nitride sheet

    NASA Astrophysics Data System (ADS)

    Li, J.; Wang, H.; Hu, J.; Wu, R. Q.

    2016-05-01

    Structural and magnetic properties of many transition-metal dimers embedded in a defected hexagonal boron nitride monolayer are investigated through density functional calculations to search for systems with magnetic anisotropy energies (MAEs) larger than 30meV. In particular, Ir-Ir@Dh-BN is found to have both large MAE (˜126 meV) and high structural stability against dissociation and diffusion, and it hence can serve as magnetic unit in spintronics and quantum computing devices. This giant MAE mainly results from the spin orbit coupling and the magnetization of the upper Ir atom, which is in a rather isolated environment.

  11. 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.

  12. The far-ultraviolet spectra of transition metal complexes

    NASA Astrophysics Data System (ADS)

    Sandorfy, C.; Lussier, L. S.; Richer, G.; Goursot, A.; Pénigault, E.; Weber, J.

    1986-03-01

    The intense bands which are found beyond the d-d bands in the electronic absorption spectra of transition metal complexes are usually assigned to intra-ligand or charge transfer transitions. However, Rydberg transitions originating with either the mainly 3d or ligand orbitals are also expected to contribute in this part of the spectrum. To explore this the vapor phase electronic absorption spectra of the tri-hexafluoroacetyl-acetonate complexes of Al, Sc, V, Cr, Fe and Mn have been recorded up to about 80000 cm -1. In order to locate the Rydberg bands, quantum chemical calculations were carried out using the multiple scattering Xα MO method. Among the 4p and 4f type Rydberg bands there are several which are spin, Laporte, symmetry and angular momentum allowed and are expected to contribute strongly to the intensity observed in the ultraviolet and far-ultraviolet parts of the spectrum. The corresponding Rydberg states can mix, however, with valence-shell states of the same symmetry. The far-ultraviolet spectra of three sandwich compounds: bicyclopentadienyl Fe, Co and Ni were also determined. Due to the very low ionization potentials of these compunds, Rydberg transitions can contribute to the observed bands at rather low frequencies.

  13. Weldability of thin sheet metals by small-scale resistance spot welding using high-frequency inverter and capacitor-discharge power supplies

    NASA Astrophysics Data System (ADS)

    Zhou, Y.; Dong, S. J.; Ely, K. J.

    2001-08-01

    An investigation has been conducted of the weldability of 0.2-mm-thick sheet aluminum, brass, and copper in small-scale resistance spot welding using a high-frequency inverter and a capacitor-discharge power supply. The results have been compared to those of previous investigations using a line-frequency alternating current power supply. The effects of electrode materials and process parameters on joint strength, nugget diameter, weld-metal expulsion and electrode-sheet sticking were studied. This work has also provided practical guidelines for selection of power supplies, process parameters (welding current/pulse energy, welding time/pulse width, electrode forces, etc.) and electrode materials for small-scale resistance spot welding of thin sheet aluminum, brass and copper.

  14. Size Effects in Thin Face-Centered Cubic Metals for Different Complex Forming Loadings

    NASA Astrophysics Data System (ADS)

    Dubos, Pierre-Antoine; Hug, Eric; Thibault, Simon; Ben Bettaieb, Mohamed; Keller, Clément

    2013-12-01

    Influence of the size effects on the mechanical behavior of face-centered cubic metals was studied for complex loadings close to microforming ones. The effect of a reduction in thickness ( t) over grain size ( d) ratio on the mechanical behavior for high-purity nickel and copper is investigated for three different loadings by tensile and Nakazima tests (plane strain conditions and balanced biaxial expansion). Experimental results highlight a strong degradation of the mechanical properties of Cu and Ni when the t/ d ratio is reduced below a critical value, independently of the strain path. However, this effect occurs if the equivalent plastic strain is larger than a critical level which is strain path dependent and related to the stress triaxiality. The current study reveals that plastic anisotropy is also affected by size effects. An excellent correlation is obtained between the t/ d ratio and the thickness reduction, through the mean normal plastic anisotropy parameter which is widely used to estimate sheet formability. A size effect map based on forming limit diagrams is proposed to depict the optimal conditions of microforming.

  15. Mechanical Characterization of Adhesive Bonded Sheet Metal Joints at Elevated Temperature

    NASA Astrophysics Data System (ADS)

    Mori, Kiyomi; Azimin, Muhd; Tanaka, Masashi; Ikeda, Takashi

    A new approach is expected for heat resisting metal joints with inorganic adhesive. In the present study, the mechanical characterization of the inorganic adhesive and the strength evaluation of metal joints are realized by an experimental procedure that includes a static test for single lap joints bonded with inorganic adhesives. The inorganic adhesive can be cured at 150°C, and the maximum temperature resistance proposed is up to 1,200°C. A tensile shear test for the joints with a nickel adherend is performed at an elevated temperature of up to 400°C. The effect of material property, overlap length, and thickness of adherend on the joint strength is discussed based on stress analysis for corresponding joint models using a Finite Element Method. It is important to confirm whether fracture occurred in the adhesive layer or at the interface between the adhesive and the adherend. Therefore, the deformation and fracture behavior of the adhesive layer is investigated microscopically by the photographs of a scanning electron microscope (SEM) for the fracture surface.

  16. Numerical Investigations on the Influence of Superimposed Double-Sided Pressure on the Formability of Biaxially Stretched AA6111-T4 Sheet Metal

    NASA Astrophysics Data System (ADS)

    Liu, Jianguang; Wang, Zhongjin; Meng, Qingyuan

    2012-04-01

    Lightweight materials have been widely used in aerospace, automobile industries to meet the requirement of structural weight reduction. Due to their limited plasticity at room temperature, however, lightweight materials always exhibit distinctly poor forming capability in comparison with conventional deep drawing steels. Based on the phenomenon that the superimposed hydrostatic pressure can improve the plasticity of metal, many kinds of double-sided pressure forming processes have been proposed. In the present study, the Gurson-Tvergaard-Needleman (GTN) damage model combined with finite element method is used to investigate the influence of double-sided pressure on the deformation behavior of biaxially stretched AA6111-T4 sheet metal, including nucleation and growth of microvoids, evaluation of stress triaxiality, and so forth. The Marciniak-Kuczynski (M-K) localized necking model is used to predict the right-hand side of the forming limit diagram (FLD) of sheet metal under superimposed double-sided pressure. It is found that the superimposed double-sided pressure has no obvious effect on the nucleation of microvoids. However, the superimposed double-sided pressure can suppress the growth and coalescence of microvoids. The forming limit curve (FLC) of the biaxially stretched AA6111-T4 sheet metal under the superimposed double-sided pressure is improved and the fracture locus shifts to the left. Furthermore, the formability increase value is sensitive to the strain path.

  17. Metal-metal interaction in Fischer carbene complexes: a study of ferrocenyl and biferrocenyl tungsten alkylidene complexes.

    PubMed

    van der Westhuizen, Belinda; Speck, J Matthäus; Korb, Marcus; Friedrich, Joachim; Bezuidenhout, Daniela I; Lang, Heinrich

    2013-12-16

    A series of ferrocenyl (Fc = ferrocenyl; fc = ferrocen-1,1'-diyl) and biferrocenyl (Bfc = 1',1″-biferrocenyl; bfc = 1',1″-biferrocen-1,1‴-diyl) mono- and biscarbene tungsten(0) complexes of the type [(CO)5W═C(OMe)R] (1, R = Fc; 3, R = Bfc) and [(CO)5W═C(OMe)-R'-(OMe)C═W(CO)5] (2, R' = fc; 4, R' = bfc) were synthesized according to the classical synthetic methodology by reacting W(CO)6 with LiR (R = Fc, fc, bfc), followed by a subsequent alkylation using methyl trifluoromethanesulfonate. Electrochemical investigations were carried out on these complexes to get a closer insight into the electronic properties of 1-4. The ferrocenyl and biferrocenyl moieties in 1-4 show reversible one-electron redox events. It was further found that the Fischer carbene unit is reducible in an electrochemical one-electron transfer process. For the tungsten carbonyl moieties, irreversible oxidation processes were found. In addition, charge transfer studies were performed on 1-4 using in situ UV-vis-NIR and infrared spectroelectrochemical techniques. During the UV-vis-NIR investigations, typical low energy transitions for the mixed-valent biferrocenyl unit were found. A further observed high energy NIR absorption is attributed to a metal-metal charge transfer transition between the tungsten carbonyl fragment and the ferrocenyl/biferrocenyl group in the corresponding oxidized states, which can be described as class II systems according to Robin and Day. This assignment was verified by infrared spectroelectrochemical studies. The electrochemical investigations are supported by density functional theory calculations. The structural properties of 1-4 in the solid state were investigated by single-crystal X-ray diffraction studies showing no substituent effects on bond lengths and angles. The biferrocenyl derivatives exhibit syn-conformation of the ferrocenyl and carbene building blocks.

  18. 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.

  19. Antimicrobial Activity of Metal & Metal Oxide Nanoparticles Interfaced With Ligand Complexes Of 8-Hydroxyquinoline And α-Amino Acids

    NASA Astrophysics Data System (ADS)

    Bhanjana, Gaurav; Kumar, Neeraj; Thakur, Rajesh; Dilbaghi, Neeraj; Kumar, Sandeep

    2011-12-01

    Antimicrobial nanotechnology is a recent addition to the fight against disease causing organisms, replacing heavy metals and toxins. In the present work, mixed ligand complexes of metals like zinc, silver etc. and metal oxide have been synthesized using 8-hydroxyquinoline (HQ) as a primary ligand and N-and/O-donor amino acids such as L-serine, L-alanine, glycine, cysteine and histidine as secondary ligands. These complexes were characterized using different spectroscopic techniques. The complexes were tested for antifungal and antibacterial activity by using agar well diffusion bioassay.

  20. 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.

  1. Thermal evolution and interaction between impact melt sheet and footwall: A genetic model for the contact sublayer of the Sudbury Igneous Complex, Canada

    NASA Astrophysics Data System (ADS)

    Prevec, Stephen A.; Cawthorn, R. Grant

    2002-08-01

    The Sudbury Igneous Complex (SIC) and associated Ni-Cu-PGE mineralization has been interpreted in terms of a large meteorite impact event. In this study, the thermal relationship between the large cooling melt sheet and the surrounding country rock is examined in terms of its role in an evolving thermal gradient rather than as a passive receptacle for the melt sheet above. Thermal modeling of this environment is undertaken using physical and thermal constraints appropriate to the SIC and assuming heat dissipation from the 2.5-km-thick superheated melt sheet (>=1800°C) by either diffusion with zero convection or by rapid convection within the melt sheet. With zero convection, basal cooling produces a solid base, which lowers conductivity such that the immediate footwall rocks reach <=1000°C, producing partial melting that extends 200 m into the footwall. In a rapidly convecting melt sheet the initial footwall chill is remelted and high temperatures maintained within the sheet close to the contact. This results in higher temperatures being attained in the immediate footwall (1100-1200°C), inducing complete melting of proximal footwall and partial melting to depths of 500 m below the melt sheet. Proximal footwall consists of Paleoproterozoic Huronian basalts, granitoids and sediments, exposed in the south range, overlying Archaean gneisses and granitoids. Total and partial melting of this material early in the cooling history of the melt sheet and the subsequent gravitational accommodation of these melts according to density would produce a basalt-dominated basal liquid corresponding to the so-called contact sublayer. The thermal aureole predicted by our models is consistent with that preserved around the north range of the SIC assuming ~800 m of thermally induced erosion at the contact.

  2. Springback Control of Sheet Metal Forming Based on High Dimension Model Representation and Genetic Algorithm

    NASA Astrophysics Data System (ADS)

    Long, Tang; Hu, Wang; Yong, Cai; Lichen, Mao; Guangyao, Li

    2011-08-01

    Springback is related to multi-factors in the process of metal forming. In order to construct an accurate metamodel between technical parameters and springback, a general set of quantitative model assessment and analysis tool, termed high dimension model representations (HDMR), is applied to building metamodel. Genetic algorithm is also integrated for optimization based on metamodel. Compared with widely used metamodeling techniques, the most remarkable advantage of this method is its capacity to dramatically reduce sampling effort for learning the input-output behavior from exponential growth to polynomial level. In this work, the blank holding forces (BHFs) and corresponding key time are design variables. The final springback is well controlled by the HDMR-based metamodeling technique.

  3. Mica sheets with embedded metal nanorods: Chemical imaging in a topographically smooth structure

    SciTech Connect

    Graca, Malgorzata; Turner, Jeff; Marshall, Michael; Granick, Steve

    2007-09-15

    We demonstrate the concept to combine topographical smoothness and plasmonic properties to produce flat substrates with surface enhanced Raman spectroscopy activity--properties that may find use in nanotribology and other thin film applications. Preliminary findings to this end are described. A dual-beam focused ion beam (FIB) system is used to drill large arrays of small pores in single crystals of mica, 2-6 {mu}m thick, yielding controlled cross sections (squares, triangles, and circles), sizes (100 nm to many microns), and arrangements (square, hexagonal, and random). When filled with metals, arrays result to embedded nanorods with their long axis oriented normal to the surface. As an extension of this method, arrays of nanorods standing perpendicular to a supporting surface can also be produced.

  4. Effect of strain rate on shear properties and fracture characteristics of DP600 and AA5182-O sheet metal alloys

    NASA Astrophysics Data System (ADS)

    Rahmaan, Taamjeed; Butcher, Cliff; Abedini, Armin; Worswick, Michael

    2015-09-01

    Shear tests were performed at strain rates ranging from quasi-static (.01 s-1) to 600 s-1 for DP600 steel and AA5182-O sheet metal alloys at room temperature. A miniature sized shear specimen was modified and validated in this work to perform high strain rate shear testing. Digital image correlation (DIC) techniques were employed to measure the strains in the experiments, and a criterion to detect the onset of fracture based on the hardening rate of the materials is proposed. At equivalent strains greater than 20%, the DP600 and AA5182 alloys demonstrated a reduced work hardening rate at elevated strain rates. At lower strains, the DP600 shows positive rate sensitivity while the AA5182 was not sensitive to strain rate. For both alloys, the equivalent fracture strain and elongation to failure decreased with strain rate. A conversion of the shear stress to an equivalent stress using the von Mises yield criterion provided excellent agreement with the results from tensile tests at elevated strain rates. Unlike the tensile test, the shear test is not limited by the onset of necking so the equivalent stress can be determined over a larger range of strain.

  5. Effects of heat input on mechanical properties of metal inert gas welded 1.6 mm thick galvanized steel sheet

    NASA Astrophysics Data System (ADS)

    Rafiqul, M. I.; Ishak, M.; Rahman, M. M.

    2012-09-01

    It is usually a lot easier and less expensive to galvanize steel before it is welded into useful products. Galvanizing afterwards is almost impossible. In this research work, Galvanized Steel was welded by using the ER 308L stainless steel filler material. This work was done to find out an alternative way of welding and investigate the effects of heat input on the mechanical properties of butt welded joints of Galvanized Steel. A 13.7 kW maximum capacity MIG welding machine was used to join 1.6 mm thick sheet of galvanized steel with V groove and no gap between mm. Heat inputs was gradually increased from 21.06 to 25.07 joules/mm in this study. The result shows almost macro defects free welding and with increasing heat input the ultimate tensile strength and welding efficiency decrease. The Vickers hardness also decreases at HAZ with increasing heat input and for each individual specimen; hardness was lowest in heat affected zone (HAZ), intermediate in base metal and maximum in welded zone. The fracture for all specimens was in the heat affected zone while testing in the universal testing machine.

  6. 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.

  7. 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.

  8. Forming of a super plastic sheet metal made of MgAZ31 alloy

    NASA Astrophysics Data System (ADS)

    Zaid, Adnan I. O.; Al-Matari, Mustafa A. A.; Nazzal, M. A. H.

    2016-08-01

    Metal forming industries are constantly looking for advanced innovation, economical and energy efficient techniques. Superplastic forming has a great potential to be one of those advanced forming methods. It is a near net shape forming process which uses a unique type of materials where elongation exceeds 200% during a controlled forming conditions, e.g. temperature, pressure, and strain rate. Most of superplastic materials are formed by gas technique at elevated temperature. The main objectives of the research work in this paper were: to study the effects of the forming schemes on the forming time and thickness distribution of the formed and device a method to improve the forming part thickness and its uniformity distribution and the forming time. In this paper, a hydraulic and heating system were designed and manufactured to facilitate the experimental investigation. The superplastic magnesium alloy AZ31, Mg AZ31, was formed at 350°C with different strain rates to investigate the effect of the forming pressure profiles on the thickness uniformity of the superplastic formed part. The pressure profiles were generated based on Dutta and Mukherjee analytical approach. Finally, a variable strain rate method is modified to improve the uniformity of the thickness distribution of the formed part and reduce the forming time; which is a major limitation of superplastic forming.

  9. Transition metal complexes of a salen-fullerene diad: redox and catalytically active nanostructures for delivery of metals in nanotubes.

    PubMed

    Lebedeva, Maria A; Chamberlain, Thomas W; Davies, E Stephen; Mancel, Dorothée; Thomas, Bradley E; Suyetin, Mikhail; Bichoutskaia, Elena; Schröder, Martin; Khlobystov, Andrei N

    2013-09-01

    A covalently-linked salen-C60 (H2L) assembly binds a range of transition metal cations in close proximity to the fullerene cage to give complexes [M(L)] (M=Mn, Co, Ni, Cu, Zn, Pd), [MCl(L)] (M=Cr, Fe) and [V(O)L]. Attaching salen covalently to the C60 cage only marginally slows down metal binding at the salen functionality compared to metal binding to free salen. Coordination of metal cations to salen-C60 introduces to these fullerene derivatives strong absorption bands across the visible spectrum from 400 to 630 nm, the optical features of which are controlled by the nature of the transition metal. The redox properties of the metal-salen-C60 complexes are determined both by the fullerene and by the nature of the transition metal, enabling the generation of a wide range of fullerene-containing charged species, some of which possess two or more unpaired electrons. The presence of the fullerene cage enhances the affinity of these complexes for carbon nanostructures, such as single-, double- and multiwalled carbon nanotubes and graphitised carbon nanofibres, without detrimental effects on the catalytic activity of the metal centre, as demonstrated in styrene oxidation catalysed by [Cu(L)]. This approach shows promise for applications of salen-C60 complexes in heterogeneous catalysis.

  10. 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...

  11. Scalable synthesis of layer-controlled WS{sub 2} and MoS{sub 2} sheets by sulfurization of thin metal films

    SciTech Connect

    Orofeo, Carlo M.; Suzuki, Satoru; Sekine, Yoshiaki; Hibino, Hiroki

    2014-08-25

    Transition metal dichalcogenides (TMDs) have emerged as exciting 2D materials beyond graphene due to their promising applications in the field of electronics and optoelectronics. Hence, the ability to produce controllable and uniformly thick TMD sheets over a large area is of utmost important for large-scale applications. Here, a facile method of synthesizing large-area, layer-controlled WS{sub 2}, and MoS{sub 2} sheets by sulfurization of their corresponding thin metal films is reported. A metal film, which is deposited by magnetron sputtering method, can be adjusted to produce, with great control, the desired sheet thickness down to a monolayer. Various characterization techniques, such as Raman, photoluminescence, and transmission electron microscopy, were used to evaluate the grown films. The results confirmed some of the exotic properties of TMDs such as the thickness dependent band-gap transition (indirect to direct band gap) and Raman shift. Devices made directly on the as-grown film showed modest mobility, ranging from 0.005 to 0.01 cm{sup 2} V{sup −1}s{sup −1}. Our synthesis method is simple and could also be used to synthesize other TMDs.

  12. 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

  13. Experimental and theoretical studies on arene-bridged metal-metal-bonded dimolybdenum complexes.

    PubMed

    Carrasco, Mario; Curado, Natalia; Álvarez, Eleuterio; Maya, Celia; Peloso, Riccardo; Poveda, Manuel L; Rodríguez, Amor; Ruiz, Eliseo; Álvarez, Santiago; Carmona, Ernesto

    2014-05-12

    The bis(hydride) dimolybdenum complex, [Mo2(H)2{HC(N-2,6-iPr2C6H3)2}2(thf)2], 2, which possesses a quadruply bonded Mo2(II) core, undergoes light-induced (365 nm) reductive elimination of H2 and arene coordination in benzene and toluene solutions, with formation of the Mo(I)2 complexes [Mo2{HC(N-2,6-iPr2C6H3)2}2(arene)], 3⋅C6H6 and 3⋅C6H5Me, respectively. The analogous C6H5OMe, p-C6H4Me2, C6H5F, and p-C6H4F2 derivatives have also been prepared by thermal or photochemical methods, which nevertheless employ different Mo2 complex precursors. X-ray crystallography and solution NMR studies demonstrate that the molecule of the arene bridges the molybdenum atoms of the Mo(I)2 core, coordinating to each in an η(2) fashion. In solution, the arene rotates fast on the NMR timescale around the Mo2-arene axis. For the substituted aromatic hydrocarbons, the NMR data are consistent with the existence of a major rotamer in which the metal atoms are coordinated to the more electron-rich C-C bonds.

  14. Proposing late transition metal complexes as frustrated Lewis pairs--a computational investigation.

    PubMed

    Pal, Amrita; Vanka, Kumar

    2013-10-14

    There has been considerable interest in recent times to develop transition metal complex systems that can demonstrate metal-ligand cooperativity. It has recently been shown (Wass et al., J. Am. Chem. Soc., 2011, 133, 18463) that early transition metals can cooperate with ligands carrying phosphines as pendant groups, working as metal analogues to frustrated Lewis pairs (FLPs) to mediate in a variety of important reactions. What the current work attempts to do is to show how this concept of metal containing FLPs can be expanded to include late transition metal complexes as well: complexes that have been modified from existing systems that serve as efficient catalysts for homogeneous polymerization. A modified palladium complex has been considered in this regard as an example of a potential late transition metal FLP and studied with full quantum mechanical calculations. The calculations indicate that this complex would be effective at catalyzing ammonia borane dehydrogenation. The possibility of competing side reactions such as reductive elimination have also been considered, and it has been found that such processes would also yield stable products which could act as an FLP in catalyzing reactions such as the dehydrogenation of ammonia borane. The current work therefore expands the scope of metal containing FLPs to include late transition metals and demonstrates computationally the potential of such complexes for exhibiting metal-ligand cooperativity. PMID:23912196

  15. A Straightforward Electrochemical Approach to Imine‐ and Amine‐bisphenolate Metal Complexes with Facile Control Over Metal Oxidation State

    PubMed Central

    Chapman, Michael R.; Henkelis, Susan E.; Kapur, Nikil

    2016-01-01

    Abstract Synthetic methods to prepare organometallic and coordination compounds such as Schiff‐base complexes are diverse, with the route chosen being dependent upon many factors such as metal–ligand combination and metal oxidation state. In this work we have shown that electrochemical methodology can be employed to synthesize a variety of metal–salen/salan complexes which comprise diverse metal–ligand combinations and oxidation states. Broad application has been demonstrated through the preparation of 34 complexes under mild and ambient conditions. Unprecedented control over metal oxidation state (MII/III/IV where M=Fe, Mn) is presented by simple modification of reaction conditions. Along this route, a general protocol‐switch is described which allows access to analytically pure FeII/III–salen complexes. Tuning electrochemical potential, selective metalation of a Mn/Ni alloy is also presented which exclusively delivers MnII/IV–salen complexes in high yield. PMID:27547645

  16. Metallophore mapping in complex matrices by metal isotope coded profiling of organic ligands.

    PubMed

    Deicke, Michael; Mohr, Jan Frieder; Bellenger, Jean-Philippe; Wichard, Thomas

    2014-12-01

    Metal isotope coded profiling (MICP) introduces a universal discovery platform for metal chelating natural products that act as metallophores, ion buffers or sequestering agents. The detection of cation and oxoanion complexing ligands is facilitated by the identification of unique isotopic signatures created by the application of isotopically pure metals.

  17. 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.

  18. The impact of photodestruction of metal-organic complexes on transport of metals from terrestrial to aquatic ecosystems

    NASA Astrophysics Data System (ADS)

    Biryukov, Mikhail; Vladimir, Demin; Yuliya, Zavgorodnyaya; Sergey, Lapitskiy

    2014-05-01

    Biological cycles of terrestrial ecosystems involve large amounts of different metal ions from minerals composing soil and from the pools of anthropogenic origin. They are an inherent part of different energetic pathways, and constitute reactive centers of different enzymes complexes. In different cases they can play role of toxins and inhibitors and perform danger while distributing across the trophic networks. The high activity of metal ion turnover devoted to plant litter, where the autotrophic biomass is extensively decomposed by microbes. Diverse rearrangements lead to the saturated flux of intact biomolecules and complexes of metals with organic ligands (e.g. humic substances) from the plant litter to the surface waters, streams, bogs and result in their deposition and distribution in the aquatic area. In the aquatic ecosystems metal-organic complexes are involved in a new broad spectrum of biotic and abiotic pathways and interactions. Our preliminary studies have shown remarkable variation in the ferrum isotopes composition in the size fractions obtained with cascade filtration, which testifies about intensive turnover of this substances. Our study aims to study the processes occurring in the euphotic zone of the aquatic systems, predominantly the processes of photodestruction and rearrangements of metal-organic complexes under the impact of solar radiation. According to our working hypothesis, in the cascade of sequential reactions of complexe rearrangements and organic molecules degradation the metal distributes between different pools: free ions, which are available for the autotrophic and heterotrophic biota metabolism (they are highly significant for regulating the biogeochemical activity and bioproductivity of aquatic ecosystems); thermodynamically stable metal-organic complexes; precipitation and sedimentation from the solution in form of indissoluble newborn fractions. The research design is based on the laboratory-scale studies of photodestruction

  19. 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.

  20. 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…

  1. 40 CFR 721.4680 - Metal salts of complex inorganic oxyacids (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 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 oxyacids... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Metal salts of complex...

  2. 40 CFR 721.4680 - Metal salts of complex inorganic oxyacids (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 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 oxyacids... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Metal salts of complex...

  3. 40 CFR 721.4680 - Metal salts of complex inorganic oxyacids (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 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 oxyacids... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Metal salts of complex...

  4. 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)

  5. Toxicity of chlortetracycline and its metal complexes to model microorganisms in wastewater sludge.

    PubMed

    Pulicharla, Rama; Das, Ratul Kumar; Brar, Satinder Kaur; Drogui, Patrick; Sarma, Saurabh Jyoti; Verma, Mausam; Surampalli, Rao Y; Valero, Jose R

    2015-11-01

    Complexation of antibiotics with metals is a well-known phenomenon. Wastewater treatment plants contain metals and antibiotics, thus it is essential to know the effect of these complexes on toxicity towards microorganisms, typically present in secondary treatment processes. In this study, stability constants and toxicity of chlortetracycline (CTC) and metal (Ca, Mg, Cu and Cr) complexes were investigated. The calculated stability constants of CTC-metal complexes followed the order: Mg-CTC>Ca-CTC>Cu-CTC>Cr-CTC. Gram positive Bacillus thuringiensis (Bt) and Gram negative Enterobacter aerogenes (Ea) bacteria were used as model microorganisms to evaluate the toxicity of CTC and its metal complexes. CTC-metal complexes were more toxic than the CTC itself for Bt whereas for Ea, CTC and its metal complexes showed similar toxicity. In contrast, CTC spiked wastewater sludge (WWS) did not show any toxic effect compared to synthetic sewage. This study provides evidence that CTC and its metal complexes are toxic to bacteria when they are biologically available. As for WWS, CTC was adsorbed to solid part and was not biologically available to show measurable toxic effects.

  6. 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

    2015-06-01

    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.

  7. Toxicity of chlortetracycline and its metal complexes to model microorganisms in wastewater sludge.

    PubMed

    Pulicharla, Rama; Das, Ratul Kumar; Brar, Satinder Kaur; Drogui, Patrick; Sarma, Saurabh Jyoti; Verma, Mausam; Surampalli, Rao Y; Valero, Jose R

    2015-11-01

    Complexation of antibiotics with metals is a well-known phenomenon. Wastewater treatment plants contain metals and antibiotics, thus it is essential to know the effect of these complexes on toxicity towards microorganisms, typically present in secondary treatment processes. In this study, stability constants and toxicity of chlortetracycline (CTC) and metal (Ca, Mg, Cu and Cr) complexes were investigated. The calculated stability constants of CTC-metal complexes followed the order: Mg-CTC>Ca-CTC>Cu-CTC>Cr-CTC. Gram positive Bacillus thuringiensis (Bt) and Gram negative Enterobacter aerogenes (Ea) bacteria were used as model microorganisms to evaluate the toxicity of CTC and its metal complexes. CTC-metal complexes were more toxic than the CTC itself for Bt whereas for Ea, CTC and its metal complexes showed similar toxicity. In contrast, CTC spiked wastewater sludge (WWS) did not show any toxic effect compared to synthetic sewage. This study provides evidence that CTC and its metal complexes are toxic to bacteria when they are biologically available. As for WWS, CTC was adsorbed to solid part and was not biologically available to show measurable toxic effects. PMID:26119381

  8. 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

  9. Solid state pathways to complex shape evolution and tunable porosity during metallic crystal growth.

    PubMed

    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.

  10. Phosphorylation of C-H bonds of aromatic compounds using metals and metal complexes

    NASA Astrophysics Data System (ADS)

    Budnikova, Yu H.; Sinyashin, O. G.

    2015-09-01

    Key achievements and current trends in the development of methods for phosphorylation of aromatic C-H bonds catalyzed by metal salts and complexes are considered. The most important and promising approaches of the last decade, including those concerning the synthesis and properties of arylphosphonates, are distinguished. Methods for the introduction of a phosphonate group into non-activated and functionally substituted aromatic compounds and heteroaromatic molecules and phosphorylation-cyclization reactions involving acetylenes, 2-isocyanobiphenyls and alkynoates are analyzed. The possibilities of ligand-directed phosphorylation of compounds with aromatic C-H bonds and presumed mechanisms and intermediates in the C-P bond formation reactions are considered. The potential of this extensively developing research trend in organic and organoelement chemistry is highlighted. The bibliography includes 263 references.

  11. 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.

  12. 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.

  13. 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.

  14. Sensitivity Analysis of the Sheet Metal Stamping Processes Based on Inverse Finite Element Modeling and Monte Carlo Simulation

    SciTech Connect

    Yu Maolin; Du, R.

    2005-08-05

    Sheet metal stamping is one of the most commonly used manufacturing processes, and hence, much research has been carried for economic gain. Searching through the literatures, however, it is found that there are still a lots of problems unsolved. For example, it is well known that for a same press, same workpiece material, and same set of die, the product quality may vary owing to a number of factors, such as the inhomogeneous of the workpice material, the loading error, the lubrication, and etc. Presently, few seem able to predict the quality variation, not to mention what contribute to the quality variation. As a result, trial-and-error is still needed in the shop floor, causing additional cost and time delay. This paper introduces a new approach to predict the product quality variation and identify the sensitive design / process parameters. The new approach is based on a combination of inverse Finite Element Modeling (FEM) and Monte Carlo Simulation (more specifically, the Latin Hypercube Sampling (LHS) approach). With an acceptable accuracy, the inverse FEM (also called one-step FEM) requires much less computation load than that of the usual incremental FEM and hence, can be used to predict the quality variations under various conditions. LHS is a statistical method, through which the sensitivity analysis can be carried out. The result of the sensitivity analysis has clear physical meaning and can be used to optimize the die design and / or the process design. Two simulation examples are presented including drawing a rectangular box and drawing a two-step rectangular box.

  15. 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…

  16. Solvation-driven charge transfer and localization in metal complexes.

    PubMed

    Rondi, Ariana; Rodriguez, Yuseff; Feurer, Thomas; Cannizzo, Andrea

    2015-05-19

    states in an important group of molecules such as transition metal complexes is inaccurate. In particular, we proved that the solvent molecules are not just spectators of intramolecular electron density redistribution but significantly modulate it. Our results solicit further development of quantum mechanics computational methods to treat the solute and (at least) the closest solvent molecules including the nonperturbative treatment of the effects of local electrostatics and direct solvent-solute interactions to describe the dynamical changes of the solute excited states during the solvent response. PMID:25902015

  17. Antimalarial and antimicrobial activities of 8-Aminoquinoline-Uracils metal complexes

    PubMed Central

    Phopin, Kamonrat; Sinthupoom, Nujarin; Treeratanapiboon, Lertyot; Kunwittaya, Sarun; Prachayasittikul, Supaluk; Ruchirawat, Somsak; Prachayasittikul, Virapong

    2016-01-01

    8-Aminoquinoline (8AQ) derivatives have been reported to have antimalarial, anticancer, and antioxidant activities. This study investigated the potency of 8AQ-5-substituted (iodo and nitro) uracils metal (Mn, Cu, Ni) complexes (1-6) as antimalarial and antimicrobial agents. Interestingly, all of these metal complexes (1-6) showed fair antimalarial activities. Moreover, Cu complexes 2 (8AQ-Cu-5Iu) and 5 (8AQ-Cu-5Nu) exerted antimicrobial activities against Gram-negative bacteria including P. shigelloides and S. dysenteriae. The results reveal application of 8AQ and its metal complexes as potential compounds to be further developed as novel antimalarial and antibacterial agents. PMID:27103894

  18. 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.

  19. 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.

  20. 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

  1. 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

  2. A unique binding cavity for divalent cations in the DNA-metal-chromomycin A3 complex.

    PubMed

    Itzhaki, L; Weinberger, S; Livnah, N; Berman, E

    1990-02-15

    Binding of chromomycin A3 (CRA) to calf thymus DNA was investigated in the presence of divalent cations using visible absorption and 1H-nmr spectroscopies. An apparent equilibrium binding constant (approximately 10(11) M-1) was obtained from metal competition experiments using EDTA to remove the metal cation from the DNA-M-CRA (M: metal) complex. The large binding constant of the drug to DNA enabled us to obtain essentially complete complexation of CRA to the short homogeneous d(ATGCAT)2 duplex using stoichiometric amounts of the metal cation. Large induced chemical shifts were observed in the 1H-nmr spectrum of the above complex using the paramagnetic Co2+ cation, indicating that the metal occupies a unique binding site. Since no induced 1H-nmr chemical shifts were observed for the drug-Co2+ mixture, it was concluded that no metal-drug complex is formed. In addition, it was found that bound CRA is negatively charged at physiological pH and binding to the DNA could be affected only by using metal cations whose ionic radius size (less than 0.85 A) and charge (2+) were simultaneously satisfied. Stringent metal cation selectivity for the DNA-M-CRA complex may be intimately connected with the antitumor selectivity of CRA, since different types of cells generally possess widely differing molar concentrations of metal cations.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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)

  9. 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

  10. Potential levels of metal complexes of 8-hydroxyquinoline

    NASA Astrophysics Data System (ADS)

    Nishikiori, Hiromasa; Nakamura, Shogo; Natori, Daichi; Teshima, Katsuya

    2016-10-01

    The potential levels of 8-hydroxyquinoline and its titanium and zinc complexes were determined by electrochemical measurements and quantum chemical calculations. The HOMO and LUMO levels of the complexes were lower and higher than those of the iodine redox couple and titania conduction band edge, respectively. This indicated that the electrons can be transferred from the electrolyte to the titania via the complexes. The 8-hydroxyquinoline formed titanium complexes on the titania surface and formed zinc complexes in the presence of zinc ions on the surface. It is suggested that electrons were injected from the complex LUMO into the titania conduction band.

  11. 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.

  12. Heavy-metal complexation by de novo peptide design.

    PubMed

    Farrer, Brian T; Pecoraro, Vincent L

    2002-11-01

    From poisoning caused by lead-based paint on domestic buildings to groundwater contamination by naturally occurring arsenic deposits in India, heavy-metal toxicity is a global health problem. Contaminated ground water and acute cases of heavy-metal poisoning are treated with chelators to remove the heavy metals from the contaminated site or person. This review discusses the effort to generate heavy-metal chelators through peptide de novo design. De novo design entails the design of a primary sequence that will precisely fold into a predetermined secondary and tertiary protein structure. The first-generation peptide chelator used to initiate this investigation is the three-stranded coild coil containing Cys. Cys provides a potential trigonal binding site with soft thiolate ligands, which has been proposed to provide specific interactions with heavy metals. This hypothesis derives from the observation that similar sites on natural proteins show selectivity for heavy metals over other essential metals, such as Zn or Mg. A description of two systems, the TRI series and the IZ-AC peptide, is given, highlighting the interaction of these peptides with Hg, Cd, As and Pb. Arguments are also presented for the potential use of three-helix bundles as a second-generation design.

  13. Transparent volumetric three-dimensional image display based on the luminescence of a spinning sheet with dissolved Lanthanide(III) complexes.

    PubMed

    Hisatake, Shintaro; Suda, Sachio; Takahara, Jyunichi; Kobayashi, Tetsuro

    2007-05-28

    We have developed a new type of transparent volumetric three-dimensional (3D) image display in which a thin photopolymer sheet containing Lanthanide(III) complexes is used as a rotational screen. The Lanthanide(III) complexes used in our system are Eu(TTA)(3) Phen, designed for achieving red luminescence (615nm) for an excitation light of 395 nm. An arbitrary luminous point (voxel) is identified by controlling the excitation laser beam direction in synchronization with the photopolymer sheet rotation. The full colorization of the proposed volumetric 3D image display can be realized by using, for example, Eu(TTA)(3) Phen, Tb(ACAC)(3) Phen, and Coumarin 337, simultaneously.

  14. 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.

  15. 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.

  16. Determination of stability constants of aminoglycoside antibiotics with their metal complexes

    NASA Astrophysics Data System (ADS)

    Tiwow, Vanny M. A.

    2014-03-01

    One group of aminoglycoside antibiotics contains aminosugars. The aminosugar neomycin B with its derivate product neamine (2-Deoxy-4-0-(2,6-diamino-2,6-dideoxy-α-D-glucopyranosyl)-D-Streptamine) was identified as a free ligands and metal complexes. In particular, the stability constants of metal complexes by potentiometric titration techniques were investigated. Our previous study had determined the acid dissociation constants of these aminosugars with few metal complexes in fair depth. In this work, the complexation of two pyridine-containing amino alcohols and an amino sugar (neamine) have been measured potentiometrically. For instance, the stability constant of copper(II) complexation were determine and the model system generated an excellent fit. Stability constants with several metals have been determined and will be reported.

  17. Metal arene complexes in coal structure determination: Quarterly report for the period, September 1986-November 1986. [Arenetricarbonylchromium complex anion; arene iron complex anion

    SciTech Connect

    Woolsey, N.F.

    1986-12-01

    Continued investigation of arene metal (Cr, Fe) complexes for methods of ..cap alpha..-alkyl group cleavage has shown several advances during this quarter. Peroxide oxidation of an arenetricarbonylchromium complex anion has given preliminary evidence for phenol formation by methyl group removal. An arene iron complex anion was shown to react by 1,3-dipolar cycloaddition but did not show cleavage of an alkyl group from the arene ring. A postulated rhodium complex sequence where metal insertion into a carbonyl ..cap alpha.. bond provides a formal method to achieve the objectives of the proposed research when taken in conjunction with ..cap alpha..-oxidation of arene metal complex anions. All of these reactions or procedures are in their preliminary stages at present but look very promising. 2 refs.

  18. The occurrence of heavy metals in the vicinity of industrial complexes in Nigeria

    SciTech Connect

    Ndiokwere, C.L.; Ezihe, C.A. )

    1990-01-01

    The accumulation of Cd, Cr, Cu, Ni, Pb, and Zn in soils, crops, and plants as a result of industrial activities has been examined at various locations in the vicinities of steel and refinery complexes. High concentrations of the metals were recorded in all the samples from the sites close to the emission sources and the levels decreased with distance away from the sources. Considerable amounts of the metals found in the crops and plants were mainly due to aerial deposition. Soil and crop contamination by the metals was generally higher in the steel complex than the refinery. Cadmium and lead levels were particularly high in all the samples from both complexes.

  19. Asymmetric catalysis mediated by the ligand sphere of octahedral chiral-at-metal complexes.

    PubMed

    Gong, Lei; Chen, Liang-An; Meggers, Eric

    2014-10-01

    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.

  20. 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.

  1. 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

  2. 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

    2016-06-01

    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.

  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. Synthesis, characterization, antibacterial and anti-inflammatory activities of enoxacin metal complexes.

    PubMed

    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)(H(2)O)(2)]3H(2)O(M = Cu(II), Ni(II) or Mn(II)) and [M(eno)(H(2)O)(2)]Cl . 4H(2)O (M = Fe(III)) 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 Mn(II) and Cu(II) complexes exhibited potential to mediate anti-inflammatory response.

  5. 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.

  6. Nanospheres with tunable size and chirality from helical polymer-metal complexes.

    PubMed

    Freire, Félix; Seco, José Manuel; Quiñoá, Emilio; Riguera, Ricardo

    2012-11-28

    A new family of nanospheres is made by complexation of divalent metals (i.e., Ca(2+), Ba(2+)) and poly(phenylacetylene) polymers bearing α-methoxyphenylacetic acid (MPA) pendants with high content of the cis isomer responsible for their helical structures. The resulting helical polymer-metal complex (HPMC) nanospheres present two interesting properties: (a) their diameter can be tuned to different sizes, to growth or to shrink, by changing the metal ion or the polymer/metal ion ratio, and (b) the helicity on the surface and the interior of the particle can be tuned to any of the two helical senses (M or P) by selection of the metal ion. The role of the solvent, the metal ion, and the helicity of the polymer in the aggregation are discussed. The ability of these nanospheres to encapsulate is demonstrated with examples.

  7. 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.

  8. Density functional study of isoguanine tetrad and pentad sandwich complexes with alkali metal ions.

    PubMed

    Meyer, Michael; Steinke, Thomas; Sühnel, Jürgen

    2007-02-01

    Isoguanine tetraplexes and pentaplexes contain two or more stacked polyads with intercalating metal ions. We report here the results of a density functional study of sandwiched isoguanine tetrad and pentad complexes consisting of two polyads with Na(+), K(+) and Rb(+) ions at the B3LYP level. In comparison to single polyad metal ion complexes, there is a trend towards increased non-planarity of the polyads in the sandwich complexes. In general, the pentad sandwiches have relatively planar polyad structures, whereas the tetrad complexes contain highly non-planar polyad building blocks. As in other sandwich complexes and in metal ion complexes with single polyads, the metal ion-base interaction energy plays an essential role. In iG sandwich structures, this interaction energy is slightly larger than in the corresponding guanine sandwich complexes. Because the base-base interaction energy is even more increased in passing from guanine to isoguanine, the isoguanine sandwiches are thus far the only examples where the base-base interaction energy is larger than the base-metal ion interaction energy. Stacking interactions have been studied in smaller models consisting of two bases, retaining the geometry from the complete complex structures. From the data obtained at the B3LYP and BH&H levels and with Møller-Plesset perturbation theory, one can conclude that the B3LYP method overestimates the repulsion in stacked base dimers. For the complexes studied in this work, this is only of minor importance because the direct inter-tetrad or inter-pentad interaction is supplemented by a strong metal ion-base interaction. Using a microsolvation model, the metal ion preference K(+) approximately Rb(+) > Na(+) is found for tetrad complexes. On the other hand, for pentads the ordering is Rb(+) > K(+) > Na(+). In the latter case experimental data are available that agree with this prediction. PMID:17013632

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. Transverse and torsional complex vibration systems for ultrasonic seam welding of metal plates

    PubMed

    Tsujino; Ueoka; Kashino; Sugahara

    2000-03-01

    Transverse and torsional complex vibration systems for ultrasonic seam welding of metal plate specimens, using a 27 kHz complex vibration disk welding tip vibrating in transverse and torsional vibration modes, were studied. Using a complex vibration welding system with a welding tip vibrating in elliptical or circular locus, thick plate specimens can be welded with a more uniform and larger area compared to a conventional ultrasonic welding system. The disk welding tip vibrates in an elliptical or circular locus. The complex vibration system can continuously weld multiple parts of metal plate specimens such as heat sinks with a large number of fins.

  14. 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;…

  15. 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(+).

  16. 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.

  17. 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.

  18. 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.

  19. 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. PMID:16698178

  20. 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.

  1. Development of the aza-crown ether metal complexes as artificial hydrolase.

    PubMed

    Yu, Lan; Li, Fang-zhen; Wu, Jiao-yi; Xie, Jia-qing; Li, Shuo

    2016-01-01

    Hydrolases play a crucial role in the biochemical process, which can catalyze the hydrolysis of various compounds like carboxylic esters, phosphoesters, amides, nucleic acids, peptides, and so on. The design of artificial hydrolases has attracted extensive attention due to their scientific significance and potential applications in the field of gene medicine and molecular biology. Numerous macrocyclic metal complexes have been used as artificial hydrolase in the catalytic hydrolysis of the organic substrate. Aza-crown ether for this comment is a special class of the macrocyclic ligand containing both the nitrogen atoms and oxygen atoms in the ring. The studies showed that the aza-crown complexes exhibited high activity of hydrolytic enzyme. However, the aza-crown ether metal complex as artificial hydrolase is still very limited because of its difficulty in synthesis. This review summarizes the development of the aza-crown ether metal complexes as the artificial hydrolase, including the synthesis and catalysis of the transition metal complexes and lanthanide metal complexes of aza-crown ethers. The purpose of this review is to highlight: (1) the relationship between the structure and hydrolytic activity of synthetic hydrolase; (2) the synergistic effect of metal sites and ligands in the course of organic compound hydrolysis; and (3) the design strategies of the aza-crown ethers as hydrolase. PMID:26460062

  2. 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.

  3. Metal complexes with varying intramolecular hydrogen bonding networks

    PubMed Central

    Lacy, David C.; Mukherjee, Jhumpa; Lucas, Robie L.; Day, Victor W.; Borovik, A.S.

    2013-01-01

    Alfred Werner described the attributes of the primary and secondary coordination spheres in his development of coordination chemistry. To examine the effects of the secondary coordination sphere on coordination chemistry, a series of tripodal ligands containing differing numbers of hydrogen bond (H-bond) donors were used to examine the effects of H-bonds on Fe(II), Mn(II)–acetato, and Mn(III)–OH complexes. The ligands containing varying numbers of urea and amidate donors allowed for systematic changes in the secondary coordination spheres of the complexes. Two of the Fe(II) complexes that were isolated as their Bu4N+ salts formed dimers in the solid-state as determined by X-ray diffraction methods, which correlates with the number of H-bonds present in the complexes (i.e., dimerization is favored as the number of H-bond donors increases). Electron paramagnetic resonance (EPR) studies suggested that the dimeric structures persist in acetonitrile. The Mn(II) complexes were all isolated as their acetato adducts. Furthermore, the synthesis of a rare Mn(III)–OH complex via dioxygen activation was achieved that contains a single intramolecular H-bond; its physical properties are discussed within the context of other Mn(III)–OH complexes. PMID:24904193

  4. 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.

  5. 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.

  6. Facile Synthesis of Functionalized Carbene Metal Complexes from Coordinated Isonitriles.

    PubMed

    Lothschütz, Christian; Wurm, Thomas; Zeiler, Anna; Freiherr V Falkenhausen, Alexander; Rudolph, Matthias; Rominger, Frank; Hashmi, A Stephen K

    2016-02-01

    The scope and limitations of the isonitrile-based NHC template synthesis were investigated with a series of precursors containing a nucleophilic amine in combination with tethered electrophiles. In the case of alkynes and phosphonic esters as electrophiles no ring closure was observed and new functionalized NAC gold complexes were obtained. By the use of unsaturated esters and phosphonic esters as Michael acceptors in the amine precursors, ester-modified gold and palladium NHC complexes were accessible in high efficiency. PMID:26033484

  7. Labile Low-Molecular-Mass Metal Complexes in Mitochondria: Trials and Tribulations of a Burgeoning Field.

    PubMed

    Lindahl, Paul A; Moore, Michael J

    2016-08-01

    Iron, copper, zinc, manganese, cobalt, and molybdenum play important roles in mitochondrial biochemistry, serving to help catalyze reactions in numerous metalloenzymes. These metals are also found in labile "pools" within mitochondria. Although the composition and cellular function of these pools are largely unknown, they are thought to be comprised of nonproteinaceous low-molecular-mass (LMM) metal complexes. Many problems must be solved before these pools can be fully defined, especially problems stemming from the lability of such complexes. This lability arises from inherently weak coordinate bonds between ligands and metals. This is an advantage for catalysis and trafficking, but it makes characterization difficult. The most popular strategy for investigating such pools is to detect them using chelator probes with fluorescent properties that change upon metal coordination. Characterization is limited because of the inevitable destruction of the complexes during their detection. Moreover, probes likely react with more than one type of metal complex, confusing analyses. An alternative approach is to use liquid chromatography (LC) coupled with inductively coupled plasma mass spectrometry (ICP-MS). With help from a previous lab member, the authors recently developed an LC-ICP-MS approach to analyze LMM extracts from yeast and mammalian mitochondria. They detected several metal complexes, including Fe580, Fe1100, Fe1500, Cu5000, Zn1200, Zn1500, Mn1100, Mn2000, Co1200, Co1500, and Mo780 (numbers refer to approximate masses in daltons). Many of these may be used to metalate apo-metalloproteins as they fold inside the organelle. The LC-based approach also has challenges, e.g., in distinguishing artifactual metal complexes from endogenous ones, due to the fact that cells must be disrupted to form extracts before they are passed through chromatography columns prior to analysis. Ultimately, both approaches will be needed to characterize these intriguing complexes and to

  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. 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.

  10. Inherent structure length in metallic glasses: Simplicity behind complexity

    DOE PAGES

    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-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

  11. Evaluation and optimization of the metal-binding properties of a complex ligand for immobilized metal affinity chromatography.

    PubMed

    Chen, Bin; Li, Rong; Li, Shiyu; Chen, Xiaoli; Yang, Kaidi; Chen, Guoliang; Ma, Xiaoxun

    2016-02-01

    The simultaneous determination of two binding parameters for metal ions on an immobilized metal affinity chromatography column was performed by frontal chromatography. In this study, the binding parameters of Cu(2+) to l-glutamic acid were measured, the metal ion-binding characteristics of the complex ligand were evaluated. The linear correlation coefficients were all greater than 99%, and the relative standard deviations of two binding parameters were 0.58 and 0.059%, respectively. The experiments proved that the frontal chromatography method was accurate, reproducible, and could be used to determine the metal-binding parameters of the affinity column. The effects of buffer pH, type, and concentration on binding parameters were explored by uniform design experiment. Regression, matching and residual analyses of the models were performed. Meanwhile, the optimum-binding conditions of Cu(2+) on the l-glutamic acid-silica column were obtained. Under these binding conditions, observations and regression values of two parameters were similar, and the observation values were the best. The results demonstrated that high intensity metal affinity column could be effectively prepared by measuring and evaluating binding parameters using frontal chromatography combined with a uniform design experiment. The present work provided a new mode for evaluating and preparing immobilized metal affinity column with good metal-binding behaviors. PMID:26632098

  12. Extremely bulky amido first row transition metal(II) halide complexes: potential precursors to low coordinate metal-metal bonded systems.

    PubMed

    Hicks, Jamie; Jones, Cameron

    2013-04-01

    Reactions of the extremely bulky potassium amide complexes, [KL'(η(6)-toluene)] or [KL"] (L'/L" = N(Ar*)(SiR3), Ar* = C6H2{C(H)Ph2}2Me-2,6,4; R = Me (L') or Ph (L")), with a series of first row transition metal(II) halides have yielded 10 rare examples of monodentate amido first row transition metal(II) halide complexes, all of which were crystallographically characterized. They encompass the dimeric, square-planar chromium complexes, [{CrL'(THF)(μ-Cl)}2] and [{CrL"(μ-Cl)}2], the latter of which displays intramolecular η(2)-Ph···Cr interactions; the dimeric tetrahedral complexes, [{ML'(THF)(μ-Br)}2] (M = Mn or Fe), [{ML"(THF)(μ-X)}2] (M = Mn, Fe or Co; X = Cl or Br) and [{CoL"(μ-Cl)}2] (which displays intramolecular η(2)-Ph···Co interactions); and the monomeric zinc amides, [L'ZnBr(THF)] (three-coordinate) and [L"ZnBr] (two-coordinate). Solution state magnetic moment determinations on all but one of the paramagnetic compounds show them to be high-spin systems. Throughout, comparisons are made with related bulky terphenyl transition metal(II) halide complexes, and the potential for the use of the prepared complexes as precursors to low-valent transition metal systems is discussed.

  13. Complexes of 3.6 kDa maltodextrin with some metals.

    PubMed

    Tomasik, Piotr; Anderegg, James W; Schilling, Christopher H

    2004-06-30

    Preparation of magnesium, lanthanum, and bismuth(III) complexes of 3.6 kDa maltodextrin and some properties of the resulting materials are presented. The metal derivatives contain metals bound to the oxygen atoms of the hydroxyl groups of maltodextrin. Additionally, the metal atoms are coordinated to the hydroxyl groups of the D-glucose units of the macroligand. Such coordination stabilized the metal - oxygen bond against hydrolysis, even in boiling water. The presence of magnesium and lanthanum atoms increased the thermal stability of maltodextrin, whereas bismuth atoms decreased it.

  14. DNA binding mode of transition metal complexes, a relationship to tumor cell toxicity.

    PubMed

    Ashfaq, M; Najam, T; Shah, S S A; Ahmad, M M; Shaheen, S; Tabassum, R; Rivera, G

    2014-01-01

    Transition metal-based compounds constitute a distinct class of chemotherapeutics extensively used in the clinic as antitumor and antiviral agents. However, drug resistance and side effects of established antitumor metallodrugs such as cisplatin [cis-diamminedichloroplatinum(II)] and its analogues, carboplatin and oxaliplatin, have limited their clinical utility. These limitations have prompted a search for more effective and less toxic metal-based antitumor agents. The unique properties of metal ions, such as redox transfer/electron shuttling, and versatile coordination geometries arising from various oxidation states, result in metal ions and complexes that have potential medicinal applications that could be complementary to organic compounds and which are widely sought in drug discovery efforts. This review summarizes the results that show that transition metal complexes exhibit antitumor effects that differ from cisplatin or its analogues.

  15. Metal ion complexation by ionizable crown ethers. Progress report, January 1, 1991--December 31, 1993

    SciTech Connect

    Bartsch, R.A.

    1993-07-01

    Cyclic and acyclic polyether compounds with pendent carboxylic acid, phosphonic acid monoethyl ester, sulfonic acid, phosphinic acid and hydroxamic acid groups have been synthesized. The proton-ionizable polyethers can come with and without lipophilic groups. Two types of lipophilic di-ionizable lariat ethers have been prepared. Conformations of proton-ionizable lariat ethers have been probed. Competitive alkali metal cation transport by syn-(decyl)dibenzo-16-crown-5-oxyacetic acid and lipophilic proton-ionizable dibenzo lariat ethers in polymer-supported liquid membranes was studied. Complexation of alkali metal cations with ionized lariat ethers was studied. Condensation polymerization of cyclic and acyclic dibenzo polyethers containing pendent mono-ionizable groups with formaldehyde produces novel ion exchange resins with both ion exchange sites for metal ion complexation and polyether binding sites for metal ion recognition. Resins prepared from lariat ether dibenzo phosphonic acid monoethyl esters show strong sorption of divalent heavy metal cations with selectivity for Pb{sup 2+}.

  16. Electroscopy Ionization Photoelectron Spectroscopy: Probing the Electronic Structure of Inorganic Metal Complexes in the Gas Phase

    SciTech Connect

    Waters, Tom; Wang, Xue B.; Wang, Lai S.

    2007-02-01

    The coupling of electrospray to photoelectron spectroscopy has allowed a number of negatively charged solution phase transition metal complexes to be transferred to the gas phase and studied by photoelectron spectroscopy for the first time. Experiments have been performed on a range of species, including classic square-planar and octahedral transition-metal halide complexes, metal-metal bonded species, transition metal bis(dithiolene) centers and a variety of mononuclear and polynuclear iron-sulfur clusters that are related to important bioinorganic centers. The studies have provided detailed information about the electronic structure and molecular orbital energy levels of these species, allowing for direct comparison with theoretical calculations, and providing insight into their intrinsic redox properties in the absence of solvation.

  17. Reverse-phase HPLC of benzylpropionitrile dithiocarbamate complexes for the determination of priority pollutant metals

    SciTech Connect

    Park, Y.J.

    1990-01-01

    A new dithiocarbamate, benzylpropionitrile dithiocarbamate (BPDTC), has been synthesized for use in metal analysis. The HPLC behavior of metal chelates of BPDTC has been investigated for the simultaneous determination of antimony, cadmium, chromium, copper, mercury, nickel, lead, selenium, thallium, and zinc, all of which are on the Environmental Protection Agency's list of priority pollutant metals. Metals are extracted into dichloromethane as BPDTC chelates, and then separated on a C-18 column. Cobalt is added as an internal standard. The effects of pH and of three organic modifiers (methanol, acetonitrile, tetrahydrofuran) of the mobile phase on retention time have been investigated. Addition of dichloromethane to the mobile phase increases solubility and chelate stability, and improves the separation of metal BPDTC complexes. BPDTC is added to the aqueous mobile phase to reduce on-column dissociation of the complexes. Detection limits at 260 nm are in the range of 0.1 to 3 ppb using a 1 liter sample.

  18. Complexation of trace metals by adsorbed natural organic matter

    USGS Publications Warehouse

    Davis, J.A.

    1984-01-01

    The adsorption behavior and solution speciation of Cu(II) and Cd(II) were studied in model systems containing colloidal alumina particles and dissolved natural organic matter. At equilibrium a significant fraction of the alumina surface was covered by adsorbed organic matter. Cu(II) was partitioned primarily between the surface-bound organic matter and dissolved Cu-organic complexes in the aqueous phase. Complexation of Cu2+ with the functional groups of adsorbed organic matter was stronger than complexation with uncovered alumina surface hydroxyls. It is shown that the complexation of Cu(II) by adsorbed organic matter can be described by an apparent stability constant approximately equal to the value found for solution phase equilibria. In contrast, Cd(II) adsorption was not significantly affected by the presence of organic matter at the surface, due to weak complex formation with the organic ligands. The results demonstrate that general models of trace element partitioning in natural waters must consider the presence of adsorbed organic matter. ?? 1984.

  19. Correlation between oxygen adsorption energy and electronic structure of transition metal macrocyclic complexes

    NASA Astrophysics Data System (ADS)

    Liu, Kexi; Lei, Yinkai; Wang, Guofeng

    2013-11-01

    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 O2 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 N4 chelation, as well as the molecular and electronic structures for the O2 adsorption on these macrocyclic molecules, using the density functional theory calculation method. We found that the calculated adsorption energy of O2 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_{z^2 }, d_{xy}, d_{xz}, and dyz) 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 O2 adsorption energy for enhancing the ORR activity of transition metal macrocyclic complex catalysts.

  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.