Sample records for complex sheet metal

  1. Rubber pad forming - Efficient approach for the manufacturing of complex structured sheet metal blanks for food industry

    NASA Astrophysics Data System (ADS)

    Spoelstra, Paul; Djakow, Eugen; Homberg, Werner

    2017-10-01

    The production of complex organic shapes in sheet metals is gaining more importance in the food industry due to increasing functional and hygienic demands. Hence it is necessary to produce parts with complex geometries promoting cleanability and general sanitation leading to improvement of food safety. In this context, and especially when stainless steel has to be formed into highly complex geometries while maintaining desired surface properties, it is inevitable that alternative manufacturing processes will need to be used which meet these requirements. Rubber pad forming offers high potential when it comes to shaping complex parts with excellent surface quality, with virtually no tool marks and scratches. Especially in cases where only small series are to be produced, rubber pad forming processes offers both technological and economic advantages. Due to the flexible punch, variation in metal thickness can be used with the same forming tool. The investments to set-up Rubber pad forming is low in comparison to conventional sheet metal forming processes. The process facilitates production of shallow sheet metal parts with complex contours and bends. Different bending sequences in a multiple tool set-up can also be conducted. The planned contribution thus describes a brief overview of the rubber pad technology. It shows the prototype rubber pad forming machine which can be used to perform complex part geometries made from stainless steel (1.4301). Based on an analysis of the already existing systems and new machines for rubber pad forming processes, together with their process properties, influencing variables and areas of application, some relevant parts for the food industry are presented.

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

    ERIC Educational Resources Information Center

    Dade County Public Schools, Miami, FL.

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

  3. 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.

  4. 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.

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

    PubMed

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

    2011-12-06

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

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. Synthesis of Metal Phthalocyanine Sheet Polymers

    NASA Technical Reports Server (NTRS)

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

    1986-01-01

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

  12. 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.

  13. 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…

  14. Large patternable metal nanoparticle sheets by photo/e-beam lithography

    NASA Astrophysics Data System (ADS)

    Saito, Noboru; Wang, Pangpang; Okamoto, Koichi; Ryuzaki, Sou; Tamada, Kaoru

    2017-10-01

    Techniques for micro/nano-scale patterning of large metal nanoparticle sheets can potentially be used to realize high-performance photoelectronic devices because the sheets provide greatly enhanced electrical fields around the nanoparticles due to localized surface plasmon resonances. However, no single metal nanoparticle sheet currently exists with sufficient durability for conventional lithographical processes. Here, we report large photo and/or e-beam lithographic patternable metal nanoparticle sheets with improved durability by incorporating molecular cross-linked structures between nanoparticles. The cross-linked structures were easily formed by a one-step chemical reaction; immersing a single nanoparticle sheet consisting of core metals, to which capping molecules ionically bond, in a dithiol ethanol solution. The ligand exchange reaction processes were discussed in detail, and we demonstrated 20 μm wide line and space patterns, and a 170 nm wide line of the silver nanoparticle sheets.

  15. 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,…

  16. Aircraft Sheet Metal General Repairs; Sheet Metal Work 3: 9857.01.

    ERIC Educational Resources Information Center

    Dade County Public Schools, Miami, FL.

    The outline will serve as a guide to the high school student interested in the field of sheet metal work. Intended for the 12th grade level, the course is organized into three instructional blocks: (1) general repairs, (2) line maintenance, (3) brazing and soldering, followed by a posttest. The advanced course is 135 hours in length and offers…

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

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

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

  18. 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

  19. Stiffness management of sheet metal parts using laser metal deposition

    NASA Astrophysics Data System (ADS)

    Bambach, Markus; Sviridov, Alexander; Weisheit, Andreas

    2017-10-01

    Tailored blanks are established solutions for the production of load-adapted sheet metal components. In the course of the individualization of production, such semi-finished products are gaining importance. In addition to tailored welded blanks and tailored rolled blanks, patchwork blanks have been developed which allow a local increase in sheet thickness by welding, gluing or soldering patches onto sheet metal blanks. Patchwork blanks, however, have several limitations, on the one hand, the limited freedom of design in the production of patchwork blanks and, on the other hand, the fact that there is no optimum material bonding with the substrate. The increasing production of derivative and special vehicles on the basis of standard vehicles, prototype production and the functionalization of components require solutions with which semi-finished products and sheet metal components can be provided flexibly with local thickenings or functional elements with a firm metallurgical bond to the substrate. An alternative to tailored and patchwork blanks is, therefore, a free-form reinforcement applied by additive manufacturing via laser metal deposition (LMD). By combining metal forming and additive manufacturing, stiffness can be adapted to the loads based on standard components in a material-efficient manner and without the need to redesign the forming tools. This paper details a study of the potential of stiffness management by LMD using a demonstrator part. Sizing optimization is performed and part distortion is taken into account to find an optimal design for the cladding. A maximum stiffness increase of 167% is feasible with only 4.7% additional mass. Avoiding part distortion leads to a pareto-optimal design which achieves 95% more stiffness with 6% added mass.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Winklhofer, Johannes; Trattnig, Gernot; Lind, Christoph

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

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

    DOEpatents

    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.

  3. Numerical analysis of thermal drilling technique on titanium sheet metal

    NASA Astrophysics Data System (ADS)

    Kumar, R.; Hynes, N. Rajesh Jesudoss

    2018-05-01

    Thermal drilling is a technique used in drilling of sheet metal for various applications. It involves rotating conical tool with high speed in order to drill the sheet metal and formed a hole with bush below the surface of sheet metal. This article investigates the finite element analysis of thermal drilling on Ti6Al4Valloy sheet metal. This analysis was carried out by means of DEFORM-3D simulation software to simulate the performance characteristics of thermal drilling technique. Due to the contribution of high temperature deformation in this technique, the output performances which are difficult to measure by the experimental approach, can be successfully achieved by finite element method. Therefore, the modeling and simulation of thermal drilling is an essential tool to predict the strain rate, stress distribution and temperature of the workpiece.

  4. 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.

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

    ERIC Educational Resources Information Center

    Shibayama, Guy T.

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

  6. Laser Indirect Shock Welding of Fine Wire to Metal Sheet

    PubMed Central

    Wang, Xiao; Huang, Tao; Luo, Yapeng; Liu, Huixia

    2017-01-01

    The purpose of this paper is to present an advanced method for welding fine wire to metal sheet, namely laser indirect shock welding (LISW). This process uses silica gel as driver sheet to accelerate the metal sheet toward the wire to obtain metallurgical bonding. A series of experiments were implemented to validate the welding ability of Al sheet/Cu wire and Al sheet/Ag wire. It was found that the use of a driver sheet can maintain high surface quality of the metal sheet. With the increase of laser pulse energy, the bonding area of the sheet/wire increased and the welding interfaces were nearly flat. Energy dispersive spectroscopy (EDS) results show that the intermetallic phases were absent and a short element diffusion layer which would limit the formation of the intermetallic phases emerging at the welding interface. A tensile shear test was used to measure the mechanical strength of the welding joints. The influence of laser pulse energy on the tensile failure modes was investigated, and two failure modes, including interfacial failure and failure through the wire, were observed. The nanoindentation test results indicate that as the distance to the welding interface decreased, the microhardness increased due to the plastic deformation becoming more violent. PMID:28895900

  7. Laser Indirect Shock Welding of Fine Wire to Metal Sheet.

    PubMed

    Wang, Xiao; Huang, Tao; Luo, Yapeng; Liu, Huixia

    2017-09-12

    The purpose of this paper is to present an advanced method for welding fine wire to metal sheet, namely laser indirect shock welding (LISW). This process uses silica gel as driver sheet to accelerate the metal sheet toward the wire to obtain metallurgical bonding. A series of experiments were implemented to validate the welding ability of Al sheet/Cu wire and Al sheet/Ag wire. It was found that the use of a driver sheet can maintain high surface quality of the metal sheet. With the increase of laser pulse energy, the bonding area of the sheet/wire increased and the welding interfaces were nearly flat. Energy dispersive spectroscopy (EDS) results show that the intermetallic phases were absent and a short element diffusion layer which would limit the formation of the intermetallic phases emerging at the welding interface. A tensile shear test was used to measure the mechanical strength of the welding joints. The influence of laser pulse energy on the tensile failure modes was investigated, and two failure modes, including interfacial failure and failure through the wire, were observed. The nanoindentation test results indicate that as the distance to the welding interface decreased, the microhardness increased due to the plastic deformation becoming more violent.

  8. 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

  9. Sheet Metal Contract. Project Report Phase I with Research Findings.

    ERIC Educational Resources Information Center

    Kirkpatrick, Thomas; Sappe', Hoyt

    This report provides results of Phase I of a project that researched the occupational area of sheet metal, established appropriate committees, and conducted task verification. These results are intended to guide development of a program designed to train sheet metal workers. Section 1 contains general information: purpose of Phase I; description…

  10. 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.

  11. 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

  12. 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.

  13. 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

  14. 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.

  15. Rapid Freeform Sheet Metal Forming: Technology Development and System Verification

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kiridena, Vijitha; Verma, Ravi; Gutowski, Timothy

    The objective of this project is to develop a transformational RApid Freeform sheet metal Forming Technology (RAFFT) in an industrial environment, which has the potential to increase manufacturing energy efficiency up to ten times, at a fraction of the cost of conventional technologies. The RAFFT technology is a flexible and energy-efficient process that eliminates the need for having geometry-specific forming dies. The innovation lies in the idea of using the energy resource at the local deformation area which provides greater formability, process control, and process flexibility relative to traditional methods. Double-Sided Incremental Forming (DSIF), the core technology in RAFFT, ismore » a new concept for sheet metal forming. A blank sheet is clamped around its periphery and gradually deformed into a complex 3D freeform part by two strategically aligned stylus-type tools that follow a pre-described toolpath. The two tools, one on each side of the blank, can form a part with sharp features for both concave and convex shapes. Since deformation happens locally, the forming force at any instant is significantly decreased when compared to traditional methods. The key advantages of DSIF are its high process flexibility, high energy-efficiency, low capital investment, and the elimination of the need for massive amounts of die casting and machining. Additionally, the enhanced formability and process flexibility of DSIF can open up design spaces and result in greater weight savings.« less

  16. 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…

  17. 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.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Vivek, Anupam; Daehn, Glenn S; Taber, Geoffrey A

    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 stationarymore » 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.« less

  20. 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.

  1. Friction and lubrication modelling in sheet metal forming: Influence of lubrication amount, tool roughness and sheet coating on product quality

    NASA Astrophysics Data System (ADS)

    Hol, J.; Wiebenga, J. H.; Carleer, B.

    2017-09-01

    In the stamping of automotive parts, friction and lubrication play a key role in achieving high quality products. In the development process of new automotive parts, it is therefore crucial to accurately account for these effects in sheet metal forming simulations. This paper presents a selection of results considering friction and lubrication modelling in sheet metal forming simulations of a front fender product. For varying lubrication conditions, the front fender can either show wrinkling or fractures. The front fender is modelled using different lubrication amounts, tool roughness’s and sheet coatings to show the strong influence of friction on both part quality and the overall production stability. For this purpose, the TriboForm software is used in combination with the AutoForm software. The results demonstrate that the TriboForm software enables the simulation of friction behaviour for varying lubrication conditions, i.e. resulting in a generally applicable approach for friction characterization under industrial sheet metal forming process conditions.

  2. Phthalocyanine based metal containing porous carbon sheet

    NASA Astrophysics Data System (ADS)

    Honda, Z.; Sakaguchi, Y.; Tashiro, M.; Hagiwara, M.; Kida, T.; Sakai, M.; Fukuda, T.; Kamata, N.

    2017-03-01

    Highly-ordered fused-ring poly copper phthalocyanine (PCuPc) was prepared using copper octacyanophthalocyanine as a building block, and two-dimensional (2D) square superlattices were directly observed by the transmission electron microscopy. Remarkably, we have found a formation of polymer network that consists of a 2D porous PCuPc sheet in which the centers of phthalocyanine units are alternately occupied by Cu atom and vacancy. Using this "half-filling" PCuPc, it must be possible to create alternating arrangements for transition metal centers, and therefore control the magnetic properties of the 2D carbon sheets.

  3. 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.

  4. SHEET METAL WORKER, A SUGGESTED TRAINING COURSE.

    ERIC Educational Resources Information Center

    RONEY, MAURICE

    THE PURPOSE OF THIS CURRICULUM GUIDE IS TO ASSIST ADMINISTRATORS AND INSTRUCTORS IN PLANNING AND DEVELOPING MANPOWER DEVELOPMENT AND TRAINING PROGRAMS TO PREPARE WORKERS FOR ENTRY-LEVEL POSITIONS IN THE SHEET METAL INDUSTRY. THE MATERIAL WAS PREPARED UNDER CONTRACTUAL AGREEMENT BY OKLAHOMA STATE UNIVERSITY AND REVIEWED BY ADVISORY GROUPS. IT IS…

  5. Durability improvements of two-dimensional metal nanoparticle sheets by molecular cross-linked structures between nanoparticles

    NASA Astrophysics Data System (ADS)

    Saito, Noboru; Ryuzaki, Sou; Wang, Pangpang; Park, Susie; Sakai, Nobuyuki; Tatsuma, Tetsu; Okamoto, Koichi; Tamada, Kaoru

    2018-03-01

    The durability of two-dimensional metal nanoparticle sheets is a crucial factor for realizing next-generation optoelectronic devices based on plasmonics such as organic light-emitting diodes. Here, we report improvements in the durability of Ag nanoparticle sheets by forming alkanedithiol (DT16) cross-linked structures between the nanoparticles. The cross-linked structures in a sheet were fabricated by the self-assembly of DT16-capped Ag nanoparticles with 10% coverage (AgDT16). The durabilities for thermal, organic solvent, and oxidation reactions of AgDT16 sheets were found to be improved owing to the cross-linked structures by comparing Ag nanoparticle sheets without the cross-linked structures. The absorbance spectra revealed that the Ag nanoparticle sheets without the structure are markedly damaged by each durability test, whereas the AgDT16 sheets remain. The molecular cross-linked structures between nanoparticles in two-dimansional metal nanoparticle sheets were found to have the potential to play a key role in the realization of plasmonic optoelectronic devices including metal nanoparticles.

  6. Development of sheet-metal parabolic-trough reflector panels

    NASA Astrophysics Data System (ADS)

    Biester, A. W.

    1982-06-01

    Efforts to develop accurate, durable, and mass producible sheet metal parabolic trough solar collectors and the associated support for the collectors are described. The design considered is similar to an automobile hood, a two-piece sheet metal structure consisting of a formed steel frame or stiffening panel and a smooth contoured skin. The two pieces may be bonded or welded to form a rigid structure, and a reflective surface applied such as a film, glass mirror, or any of the presently utilized materials. The work encompassed material selection, adhesive selection and testing, tool design and fabrication, prototype panel production, and design and development of torque tube assemblies on which the trough is inclined. Results of adhesive bonding studies are given. It is found that high volume technology can be used to produce accurate and structurally sound reflector panels, and one configuration was selected for fabrication in suitable quantities for performance testing.

  7. Die Deformation Measurement System during Sheet Metal Forming

    NASA Astrophysics Data System (ADS)

    Funada, J.; Takahashi, S.; Fukiharu, H.

    2011-08-01

    In order to reduce affection to the earth environment, it is necessary to lighten the vehicles. For this purpose, high tensile steels are applied. Because of high strength, high forming force is required for producing automotive sheet metal parts. In this situation, since the dies are elastic, they are deformed during forming parts. For reducing die developing period, sheet metal forming simulation is widely applied. In the numerical simulation, rigid dies are usually used for shortening computing time. It means that the forming conditions in the actual forming and the simulation are different. It will make large errors in the results between actual forming and simulation. It can be said that if contact pressure between dies and a sheet metal in the simulation can be reproduced in the actual forming, the differences of forming results between them can also been reduced. The basic idea is to estimate die shape which can produce the same distribution as computed from simulation with rigid dies. In this study, die deformation analyses with Finite Element Method as basic technologies are evaluated. For example, simple shape and actual dies elastic contact problems were investigated. The contact width between simple shape dies was investigated. The computed solutions were in good agreement with experimental results. The one case of the actual dies in two cases was also investigated. Bending force was applied to the blank holder with a mechanical press machine. The methodology shown with applying inductive displacement sensor for measuring die deformation during applying force was also proposed.

  8. Pore-level determination of spectral reflection behaviors of high-porosity metal foam sheets

    NASA Astrophysics Data System (ADS)

    Li, Yang; Xia, Xin-Lin; Ai, Qing; Sun, Chuang; Tan, He-Ping

    2018-03-01

    Open cell metal foams are currently attracting attention and their radiative behaviors are of primary importance in high temperature applications. The spectral reflection behaviors of high-porosity metal foam sheets, bidirectional reflectance distribution function (BRDF) and directional-hemispherical reflectivity were numerically investigated. A set of realistic nickel foams with porosity from 0.87 to 0.97 and pore density from 10 to 40 pores per inch were tomographied to obtain their 3-D digital cell network. A Monte Carlo ray-tracing method was employed in order to compute the pore-level radiative transfer inside the network within the limit of geometrical optics. The apparent reflection behaviors and their dependency on the textural parameters and strut optical properties were comprehensively computed and analysed. The results show a backward scattering of the reflected energy at the foam sheet surface. Except in the cases of large incident angles, an energy peak is located almost along the incident direction and increases with increasing incident angles. Through an analytical relation established, the directional-hemispherical reflectivity can be related directly to the porosity of the foam sheet and to the complex refractive index of the solid phase as well as the specularity parameter which characterizes the local reflection model. The computations show that a linear decrease in normal-hemispherical reflectivity occurs with increasing porosity. The rate of this decrease is directly proportional to the strut normal reflectivity. In addition, the hemispherical reflectivity increases as a power function of the incident angle cosine.

  9. Incremental electrohydraulic forming - A new approach for the manufacture of structured multifunctional sheet metal blanks

    NASA Astrophysics Data System (ADS)

    Djakow, Eugen; Springer, Robert; Homberg, Werner; Piper, Mark; Tran, Julian; Zibart, Alexander; Kenig, Eugeny

    2017-10-01

    Electrohydraulic Forming (EHF) processes permit the production of complex, sharp-edged geometries even when high-strength materials are used. Unfortunately, the forming zone is often limited as compared to other sheet metal forming processes. The use of a special industrial-robot-based tool setup and an incremental process strategy could provide a promising solution for this problem. This paper describes such an innovative approach using an electrohydraulic incremental forming machine, which can be employed to manufacture the large multifunctional and complex part geometries in steel, aluminium, magnesium and reinforced plastic that are employed in lightweight constructions or heating elements.

  10. 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…

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

    NASA Astrophysics Data System (ADS)

    Xu, Da; Liu, Xuesong; Fang, Kun; Fang, Hongyuan

    2010-06-01

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

  12. Experimental analysis of the sheet metal forming behavior of newly developed press hardening steels

    NASA Astrophysics Data System (ADS)

    Meza-García, Enrique; Kräusel, Verena; Landgrebe, Dirk

    2018-05-01

    The aim of this work was the characterization of the newly developed press hardening sheet alloys 1800 PHS and 2000 PHS developed by SSAB with regard to their hot forming behavior on the basis of the experimental determination of relevant mechanical and technological properties. For this purpose conventional and non-conventional sheet metal testing methods were used. To determine the friction coefficient, the strip drawing test was applied, while the deep drawing cup test was used to determine the maximum draw depth. Finally, a V-bending test was carried out to evaluate the springback behavior of the investigated alloys by varying the blank temperature and quenching media. This work provides a technological guideline for the production of press hardened sheet parts made of these investigated sheet metals.

  13. 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.

  14. 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.

  15. 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.

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

    PubMed Central

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

    2015-01-01

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

  17. 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

  18. 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

  19. Research on NC laser combined cutting optimization model of sheet metal parts

    NASA Astrophysics Data System (ADS)

    Wu, Z. Y.; Zhang, Y. L.; Li, L.; Wu, L. H.; Liu, N. B.

    2017-09-01

    The optimization problem for NC laser combined cutting of sheet metal parts was taken as the research object in this paper. The problem included two contents: combined packing optimization and combined cutting path optimization. In the problem of combined packing optimization, the method of “genetic algorithm + gravity center NFP + geometric transformation” was used to optimize the packing of sheet metal parts. In the problem of combined cutting path optimization, the mathematical model of cutting path optimization was established based on the parts cutting constraint rules of internal contour priority and cross cutting. The model played an important role in the optimization calculation of NC laser combined cutting.

  20. 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.

  1. 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

  2. Theoretical analysis of sheet metal formability

    NASA Astrophysics Data System (ADS)

    Zhu, Xinhai

    Sheet metal forming processes are among the most important metal-working operations. These processes account for a sizable proportion of manufactured goods made in industrialized countries each year. Furthermore, to reduce the cost and increase the performance of manufactured products, in addition to the environmental concern, more and more light weight and high strength materials have been used as a substitute to the conventional steel. These materials usually have limited formability, thus, a thorough understanding of the deformation processes and the factors limiting the forming of sound parts is important, not only from a scientific or engineering viewpoint, but also from an economic point of view. An extensive review of previous studies pertaining to theoretical analyses of Forming Limit Diagrams (FLDs) is contained in Chapter I. A numerical model to analyze the neck evolution process is outlined in Chapter II. With the use of strain gradient theory, the effect of initial defect profile on the necking process is analyzed. In the third chapter, the method proposed by Storen and Rice is adopted to analyze the initiation of localized neck and predict the corresponding FLDs. In view of the fact that the width of the localized neck is narrow, the deformation inside the neck region is constrained by the material in the neighboring homogeneous region. The relative rotation effect may then be assumed to be small and is thus neglected. In Chapter IV, Hill's 1948 yield criterion and strain gradient theory are employed to obtain FLDs, for planar anisotropic sheet materials by using bifurcation analysis. The effects of the strain gradient coefficient c and the material anisotropic parameters R's on the orientation of the neck and FLDs are analyzed in a systematic manner and compared with experiments. In Chapter V, Hill's 79 non-quadratic yield criterion with a deformation theory of plasticity is used along with bifurcation analyses to derive a general analytical

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  4. 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…

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

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

    EPA Pesticide Factsheets

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

  7. 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…

  8. The transition from granite to banded aplite-pegmatite sheet complexes: An example from Megiliggar Rocks, Tregonning topaz granite, Cornwall

    NASA Astrophysics Data System (ADS)

    Breiter, K.; Ďurišová, J.; Hrstka, T.; Korbelová, Z.; Vašinová Galiová, M.; Müller, A.; Simons, B.; Shail, R. K.; Williamson, B. J.; Davies, J. A.

    2018-03-01

    The genetic relationship between a granite pluton and adjacent complex of rare-metal pegmatite-aplite-banded sheets (Megiliggar Sheet Complex - MSC) has been studied at the border of the Tregonning topaz granite at Megiliggar Rocks, Cornwall, SW England. Similarities in whole-rock chemical and mineralogical compositions, together with a gradual change in textures away from the granite margin, provide strong evidence for a genetic link between the Tregonning Granite and MSC. The sheets are likely to represent apophyses of residual melt which escaped from the largely crystallized roof of the granite pluton. The escaping melt was peraluminous, had a composition near the F, B, Li slightly enriched granite minimum, and, in comparison with other Cornish granites, was enriched in F, Li, Rb, Cs, Sn, W, Nb, Ta, and U, and depleted in Fe, Mg, Ca, Sr, Th, Zr, and REE. With increasing distance from the Tregonning Granite, the silicate melt crystallized as homogeneous leucogranite sheets and banded complex sheets (i.e. combinations of bands with granitic, aplitic and pegmatitic textures), then layered aplite-pegmatites; this sequence becoming progressively more depleted in the fluxing and volatile elements F, Li, Rb, and Cs, but showing no change in Zr/Hf ratios. The fixed Zr/Hf ratio is interpreted as indicating a direct genetic link (parental melt) between all rock types, however the melt progressively lost fluxing and volatile elements with distance from the granite pluton, probably due to wall-rock reaction or fluid exsolution and migration via fractures. Differentiation of the primary melt into Na-Li-F-rich and separate K-B-rich domains was the dominant chemical process responsible for the textural and mineral diversity of the MSC. On a large (cliff-section) scale, the proximal Na-Li-F-rich leucogranite passes through complex sheets into K-B-rich aplite-pegmatites, whilst at a smaller (<1 m) scale, the K-B-rich bands are interspersed (largely overlain) by Na

  9. Composite cell sheet for periodontal regeneration: crosstalk between different types of MSCs in cell sheet facilitates complex periodontal-like tissue regeneration.

    PubMed

    Zhang, Hao; Liu, Shiyu; Zhu, Bin; Xu, Qiu; Ding, Yin; Jin, Yan

    2016-11-14

    Tissue-engineering strategies based on mesenchymal stem cells (MSCs) and cell sheets have been widely used for periodontal tissue regeneration. However, given the complexity in periodontal structure, the regeneration methods using a single species of MSC could not fulfill the requirement for periodontal regeneration. We researched the interaction between the periodontal ligament stem cells (PDLSCs) and jaw bone marrow-derived mesenchymal stem cells (JBMMSCs), and constructed a composite cell sheet comprising both of the above MSCs to regenerate complex periodontium-like structures in nude mice. Our results show that by co-culturing PDLSCs and JBMMSCs, the expressions of bone and extracellular matrix (ECM)-related genes and proteins were significantly improved in both MSCs. Further investigations showed that, compared to the cell sheet using PDLSCs or JBMMSCs, the composite stem cell sheet (CSCS), which comprises these two MSCs, expressed higher levels of bone- and ECM-related genes and proteins, and generated a composite structure more similar to the native periodontal tissue physiologically in vivo. In conclusion, our results demonstrate that the crosstalk between PDLSCs and JBMMSCs in cell sheets facilitate regeneration of complex periodontium-like structures, providing a promising new strategy for physiological and functional regeneration of periodontal tissue.

  10. 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.

  11. Investigation of fatigue strength of tool steels in sheet-bulk metal forming

    NASA Astrophysics Data System (ADS)

    Pilz, F.; Gröbel, D.; Merklein, M.

    2018-05-01

    To encounter trends regarding an efficient production of complex functional components in forming technology, the process class of sheet-bulk metal forming (SBMF) can be applied. SBMF is characterized by the application of bulk forming operations on sheet metal, often in combination with sheet forming operations [1]. The combination of these conventional process classes leads to locally varying load conditions. The resulting load conditions cause high tool loads, which lead to a reduced tool life, and an uncontrolled material flow. Several studies have shown that locally modified tool surfaces, so-called tailored surfaces, have the potential to control the material flow and thus to increase the die filling of functional elements [2]. A combination of these modified tool surfaces and high tool loads in SBMF is furthermore critical for the tool life and leads to fatigue. Tool fatigue is hardly predictable and due to a lack of data [3], a challenge in tool design. Thus, it is necessary to provide such data for tool steels used in SBMF. The aim of this study is the investigation of the influence of tailored surfaces on the fatigue strength of the powder metallurgical tool steel ASP2023 (1.3344, AISI M3:2), which is typically used in cold forging applications, with a hardness 60 HRC ± 1 HRC. To conduct this investigation, the rotating bending test is chosen. As tailored surfaces, a DLC-coating and a surface manufactured by a high-feed-milling process are chosen. As reference a polished surface which is typical for cold forging tools is used. Before the rotating bending test, the surface integrity is characterized by measuring topography and residual stresses. After testing, the determined values of the surface integrity are correlated with the reached fracture load cycle to derive functional relations. Based on the gained results the investigated tailored surfaces are evaluated regarding their feasibility to modify tool surfaces within SBMF.

  12. 48 CFR 53.301-1427 - Standard Form 1427, Inventory Schedule A-Construction Sheet (Metals in Mill Product Form).

    Code of Federal Regulations, 2010 CFR

    2010-10-01

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

  13. 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.

  14. Finite element simulation and Experimental verification of Incremental Sheet metal Forming

    NASA Astrophysics Data System (ADS)

    Kaushik Yanamundra, Krishna; Karthikeyan, R., Dr.; Naranje, Vishal, Dr

    2018-04-01

    Incremental sheet metal forming is now a proven manufacturing technique that can be employed to obtain application specific, customized, symmetric or asymmetric shapes that are required by automobile or biomedical industries for specific purposes like car body parts, dental implants or knee implants. Finite element simulation of metal forming process is being performed successfully using explicit dynamics analysis of commercial FE software. The simulation is mainly useful in optimization of the process as well design of the final product. This paper focuses on simulating the incremental sheet metal forming process in ABAQUS, and validating the results using experimental methods. The shapes generated for testing are of trapezoid, dome and elliptical shapes whose G codes are written and fed into the CNC milling machine with an attached forming tool with a hemispherical bottom. The same pre-generated coordinates are used to simulate a similar machining conditions in ABAQUS and the tool forces, stresses and strains in the workpiece while machining are obtained as the output data. The forces experimentally were recorded using a dynamometer. The experimental and simulated results were then compared and thus conclusions were drawn.

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

    ERIC Educational Resources Information Center

    Dade County Public Schools, Miami, FL.

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

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

    EPA Pesticide Factsheets

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

  17. Deglaciation of the Eurasian ice sheet complex

    NASA Astrophysics Data System (ADS)

    Patton, Henry; Hubbard, Alun; Andreassen, Karin; Auriac, Amandine; Whitehouse, Pippa L.; Stroeven, Arjen P.; Shackleton, Calvin; Winsborrow, Monica; Heyman, Jakob; Hall, Adrian M.

    2017-08-01

    The Eurasian ice sheet complex (EISC) was the third largest ice mass during the Last Glacial Maximum with a span of over 4500 km and responsible for around 20 m of eustatic sea-level lowering. Whilst recent terrestrial and marine empirical insights have improved understanding of the chronology, pattern and rates of retreat of this vast ice sheet, a concerted attempt to model the deglaciation of the EISC honouring these new constraints is conspicuously lacking. Here, we apply a first-order, thermomechanical ice sheet model, validated against a diverse suite of empirical data, to investigate the retreat of the EISC after 23 ka BP, directly extending the work of Patton et al. (2016) who modelled the build-up to its maximum extent. Retreat of the ice sheet complex was highly asynchronous, reflecting contrasting regional sensitivities to climate forcing, oceanic influence, and internal dynamics. Most rapid retreat was experienced across the Barents Sea sector after 17.8 ka BP when this marine-based ice sheet disintegrated at a rate of ∼670 gigatonnes per year (Gt a-1) through enhanced calving and interior dynamic thinning, driven by oceanic/atmospheric warming and exacerbated by eustatic sea-level rise. From 14.9 to 12.9 ka BP the EISC lost on average 750 Gt a-1, peaking at rates >3000 Gt a-1, roughly equally partitioned between surface melt and dynamic losses, and potentially contributing up to 2.5 m to global sea-level rise during Meltwater Pulse 1A. Independent glacio-isostatic modelling constrained by an extensive inventory of relative sea-level change corroborates our ice sheet loading history of the Barents Sea sector. Subglacial conditions were predominately temperate during deglaciation, with over 6000 subglacial lakes predicted along with an extensive subglacial drainage network. Moreover, the maximum EISC and its isostatic footprint had a profound impact on the proglacial hydrological network, forming the Fleuve Manche mega-catchment which had an area of

  18. 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,…

  19. Development of oil canning index model for sheet metal forming products with large curvature

    NASA Astrophysics Data System (ADS)

    Kim, Honglae; Lee, Seonggi; Murugesan, Mohanraj; Hong, Seokmoo; Lee, Shanghun; Ki, Juncheol; Jung, Hunchul; Kim, Naksoo

    2017-09-01

    Oil canning is predominantly caused by unequal stretches and heterogeneous stress distributions in steel sheets, which affects the appearance of components and develop noise and vibration problems. This paper proposes the formulation of an Oil canning index (OCI) model that can predict the occurrence of oil canning in the sheet metal. To investigate the influence of material properties, we used electro-galvanized (EGI) and galvanized (GI) steel sheets with different thicknesses and processing conditions. Furthermore, this paper presents an appropriate experimental and numerical procedure for determining the sheet stiffness and indentation properties to evaluate the oil canning results. Experiments were carried out by varying the tensile force over different materials, thicknesses, and bead force. Comparison of the discrete results obtained from these experiments confirmed that the product shape characteristics, such as curvature, have a significant influence on the oil canning occurrence. Based on the results, we propose the new OCI model, which can effectively predict the oil canning occurrence owing to the shape curvature. Verification of the accuracy and usability of our model has been carried out by simulating the experiments that were done with the sheet metal. The authors observed a good agreement between the experimental and numerical results from the model. This research work can be considered as a very effective method for eliminating appearance defects from the automobile products.

  20. Metal Complexation in Xylem Fluid 1

    PubMed Central

    White, Michael C.; Chaney, Rufus L.; Decker, A. Morris

    1981-01-01

    The capacity of ligands in xylem fluid to form metal complexes was tested with a series of in vitro experiments using paper electrophoresis and radiographs. The xylem fluid was collected hourly for 8 hours from soybean (Glycine max L. Merr.) and tomato (Lycopersicon esculentum Mill.) plants grown in normal and Zn-phytotoxic nutrient solutions. Metal complexation was assayed by anodic or reduced cathodic movement of radionuclides (63Ni, 65Zn, 109Cd, 54Mn) that were presumed to have formed negatively charged complexes. Electrophoretic migration of Ni, Zn, Cd, and Mn added to xylem exudate and spotted on KCl- or KNO3-wetted paper showed that stable Ni, Zn, and Cd metal complexes were formed by exudate ligands. No anodic Mn complexes were observed in this test system. Solution pH, plant species, exudate collection time, and Zn phytotoxicity all affected the amount of metal complex formed in exudate. As the pH increased, there was increased anodic metal movement. Soybean exudate generally bound more of each metal than did tomato exudate. Metal binding usually decreased with increasing exudate collection time, and less metal was bound by the high-Zn exudate. Ni, Zn, Cd, and Mn in exudate added to exudate-wetted paper demonstrated the effect of ligand concentration on stable metal complex formation. Complexes for each metal were demonstratable with this method. Cathodic metal movement increased with time of exudate collection, and it was greater in the high-Zn exudate than in the normal-Zn exudate. A model study illustrated the effect of ligand concentration on metal complex stability in the electrophoretic field. Higher ligand (citric acid) concentrations increased the stability for all metals tested. Images PMID:16661666

  1. A sheet metal forming simulation of automotive outer panels considering the behavior of air in die cavity

    NASA Astrophysics Data System (ADS)

    Choi, Kwang Yong; Kim, Yun Chang; Choi, Hee Kwan; Kang, Chul Ho; Kim, Heon Young

    2013-12-01

    During a sheet metal forming process of automotive outer panels, the air trapped between a blank sheet and a die tool can become highly compressed, ultimately influencing the blank deformation and the press force. To prevent this problem, vent holes are drilled into die tools and needs several tens to hundreds according to the model size. The design and the drilling of vent holes are based on expert's experience and try-out result and thus the process can be one of reasons increasing development cycle. Therefore the study on the size, the number, and the position of vent holes is demanded for reducing development cycle, but there is no simulation technology for analyzing forming defects, making numerical sheet metal forming process simulations that incorporate the fluid dynamics of air. This study presents a sheet metal forming simulation of automotive outer panels (a roof and a body side outer) that simultaneously simulates the behavior of air in a die cavity. Through CAE results, the effect of air behavior and vent holes to blank deformation was analyzed. For this study, the commercial software PAM-STAMP{trade mark, serif} and PAM-SAFE{trade mark, serif} was used.

  2. Self-Pierce Riveting Through 3 Sheet Metal Combinations

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    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 intensivemore » 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.« less

  3. On the lightweighting of automobile engine components : forming sheet metal connecting rod

    NASA Astrophysics Data System (ADS)

    Date, P. P.; Kasture, R. N.; Kore, A. S.

    2017-09-01

    Reducing the inertia of the reciprocating engine components can lead to significant savings on fuel. A lighter connecting rod (for the same functionality and performance) with a lower material input would be an advantage to the user (customer) and the manufacturer alike. Light materials will make the connecting rod much more expensive compared to those made from steel. Non-ferrous metals are amenable to cold forging of engine components to achieve lightweighting. Alternately, one can make a hollow connecting rod formed from steel sheet, thereby making it lighter, and with many advantages over the conventionally hot forged product. The present paper describes the process of forming a connecting rod from sheet metal. Cold forming (as opposed to high energy needs, lower tool life and the need for greater number of operations and finishing processes in hot forming) would be expected to reduce the cost of manufacture by cold forming. Work hardening during forming is also expected to enhance the in-service performance of the connecting rod.

  4. Research on cutting path optimization of sheet metal parts based on ant colony algorithm

    NASA Astrophysics Data System (ADS)

    Wu, Z. Y.; Ling, H.; Li, L.; Wu, L. H.; Liu, N. B.

    2017-09-01

    In view of the disadvantages of the current cutting path optimization methods of sheet metal parts, a new method based on ant colony algorithm was proposed in this paper. The cutting path optimization problem of sheet metal parts was taken as the research object. The essence and optimization goal of the optimization problem were presented. The traditional serial cutting constraint rule was improved. The cutting constraint rule with cross cutting was proposed. The contour lines of parts were discretized and the mathematical model of cutting path optimization was established. Thus the problem was converted into the selection problem of contour lines of parts. Ant colony algorithm was used to solve the problem. The principle and steps of the algorithm were analyzed.

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

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

  6. A theoretical study on metal atom-modified BC3 sheets for effects of gas molecule adsorptions

    NASA Astrophysics Data System (ADS)

    Tang, Yanan; Cui, Xiao; Chen, Weiguang; Zhu, Dalei; Chai, Huaduo; Dai, Xianqi

    2018-06-01

    Based on the first-principle calculations, the chemical reactivity of transition metal (Fe, Co, Ni, and Cu) dopants within BC3 sheets toward toxic gas molecules (CO, NO, NO2, SO2, and HCN) is comparably investigated. First, the adsorbed gases on metal-modified BC3 sheets exhibit the different stability. Compared with other gases, the metal-modified BC3 substrates exhibit the stronger affinity toward the NO and NO2 molecules (> 1.0 eV), while the adsorbed HCN has the smallest adsorption energy, illustrating that the NO and NO2 as specific toxic gas molecule can be easily detected. Second, the adsorbed gas molecules can effectively regulate the electronic structure and magnetic property of BC3 systems. Fox example, the strong adsorption of NO and NO2 on Fe-modified BC3 systems exhibits non-magnetic property, yet these gases on Co modified BC3 systems exhibit the magnetic character. In addition, the adsorbed NO and SO2 can induce and turn the degree of magnetic moments of Ni- and Cu-modified BC3 systems. Therefore, the different kinds of adsorbed gases on metal-modified BC3 sheets can be distinguished through investigating the changed magnetic moments of system, which would provide important information for designing the functional BC3-based materials.

  7. A theoretical study on pure bending of hexagonal close-packed metal sheet

    NASA Astrophysics Data System (ADS)

    Mehrabi, Hamed; Yang, Chunhui

    2018-05-01

    Hexagonal close-packed (HCP) metals have quite different mechanical behaviours in comparison to conventional cubic metals such as steels and aluminum alloys [1, 2]. They exhibit a significant tension-compression asymmetry in initial yielding and subsequent plastic hardening. The reason for this unique behaviour can be attributed to their limited symmetric crystal structure, which leads to twining deformation [3-5]. This unique behaviour strongly influences sheet metal forming of such metals, especially for roll forming, in which the bending is dominant. Hence, it is crucial to represent constitutive relations of HCP metals for accurate estimation of bending moment-curvature behaviours. In this paper, an analytical model for asymmetric elastoplastic pure bending with an application of Cazacu-Barlat asymmetric yield function [6] is presented. This yield function considers the asymmetrical tension-compression behaviour of HCP metals by using second and third invariants of the stress deviator tensor and a specified constant, which can be expressed in terms of uniaxial yield stresses in tension and compression. As a case study, the analytical model is applied to predict the moment-curvature behaviours of AZ31B magnesium alloy sheets under uniaxial loading condition. Furthermore, the analytical model is implemented as a user-defined material through the UMAT interface in Abaqus [7, 8] for conducting pure bending simulations. The results show that the analytical model can reasonably capture the asymmetric tension-compression behaviour of the magnesium alloy. The predicted moment-curvature behaviour has good agreement with the experimental results. Furthermore, numerical results show a better accuracy by the application of the Cazacu-Barlat yield function than those using the von-Mises yield function, which are more conservative than analytical results.

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

    PubMed

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

    2016-06-10

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

  9. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  11. Tuning the p-type Schottky barrier in 2D metal/semiconductor interface:boron-sheet on MoSe2, and WSe2

    NASA Astrophysics Data System (ADS)

    Couto, W. R. M.; Miwa, R. H.; Fazzio, A.

    2017-10-01

    Van der Waals (vdW) metal/semiconductor heterostructures have been investigated through first-principles calculations. We have considered the recently synthesized borophene (Mannix et al 2015 Science 350 1513), and the planar boron sheets (S1 and S2) (Feng et al 2016 Nat. Chem. 8 563) as the 2D metal layer, and the transition metal dichalcogenides (TMDCs) MoSe2, and WSe2 as the semiconductor monolayer. We find that the energetic stability of those 2D metal/semiconductor heterojunctions is mostly ruled by the vdW interactions; however, chemical interactions also take place in borophene/TMDC. The electronic charge transfer at the metal/semiconductor interface has been mapped, where we find a a net charge transfer from the TMDCs to the boron sheets. Further electronic structure calculations reveal that the metal/semiconductor interfaces, composed by planar boron sheets S1 and S2, present a p-type Schottky barrier which can be tuned to a p-type ohmic contact by an external electric field.

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

    NASA Astrophysics Data System (ADS)

    Teixeira, P.; Santos, Abel; César Sá, J.; Andrade Pires, F.; Barata da Rocha, A.

    2007-05-01

    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.

  13. Hydrous partial melting in the sheeted dike complex at fast spreading ridges: experimental and natural observations

    NASA Astrophysics Data System (ADS)

    France, Lydéric; Koepke, Juergen; Ildefonse, Benoit; Cichy, Sarah B.; Deschamps, Fabien

    2010-11-01

    In ophiolites and in present-day oceanic crust formed at fast spreading ridges, oceanic plagiogranites are commonly observed at, or close to the base of the sheeted dike complex. They can be produced either by differentiation of mafic melts, or by hydrous partial melting of the hydrothermally altered sheeted dikes. In addition, the hydrothermally altered base of the sheeted dike complex, which is often infiltrated by plagiogranitic veins, is usually recrystallized into granoblastic dikes that are commonly interpreted as a result of prograde granulitic metamorphism. To test the anatectic origin of oceanic plagiogranites, we performed melting experiments on a natural hydrothermally altered dike, under conditions that match those prevailing at the base of the sheeted dike complex. All generated melts are water saturated, transitional between tholeiitic and calc-alkaline, and match the compositions of oceanic plagiogranites observed close to the base of the sheeted dike complex. Newly crystallized clinopyroxene and plagioclase have compositions that are characteristic of the same minerals in granoblastic dikes. Published silicic melt compositions obtained in classical MORB fractionation experiments also broadly match the compositions of oceanic plagiogranites; however, the compositions of the coexisting experimental minerals significantly deviate from those of the granoblastic dikes. Our results demonstrate that hydrous partial melting is a likely common process in the root zone of the sheeted dike complex, starting at temperatures exceeding 850°C. The newly formed melt can either crystallize to form oceanic plagiogranites or may be recycled within the melt lens resulting in hybridized and contaminated MORB melts. It represents the main MORB crustal contamination process. The residue after the partial melting event is represented by the granoblastic dikes. Our results support a model with a dynamic melt lens that has the potential to trigger hydrous partial melting

  14. Laser-assisted micro sheet forming

    NASA Astrophysics Data System (ADS)

    Holtkamp, Jens; Gillner, Arnold

    2008-01-01

    The fast growing market for micro technical products requires parts with increasing complexity. While sheet metal forming enables low cost mass production with short cycle times, it is limited by the maximum degree of deformation and the quality of the cut edge. The technology of warm forming partially eliminates these deficiencies. This operation takes place at elevated temperatures before structural transformation is initiated. It combines characteristic advantages of traditional cold and hot forming processes. Lasers as heat sources provide a high, selective and controllable energy input. The general difficulty of a uniform temperature distribution during the heating process can be reached by using an Axicon which generates an annulus on the sheet metal surface. The temperature of the workpiece, measured by a pyrometer, is tuned by a PI-Controller. A tool incorporating a multistage operation die is used for the manufacturing of up to three parts at the same time. The tool is integrated into a hydraulical press. A gearwheel made of the magnesium alloy AZ31 is chosen as metal demonstrator. The quality of these punched parts could be significantly improved at elevated temperatures

  15. Some recent developments in sheet metal forming for production of lightweight automotive parts

    NASA Astrophysics Data System (ADS)

    Tisza, M.; Lukács, Zs; Kovács, P.; Budai, D.

    2017-09-01

    Low cost manufacturing in the automotive industry is one of the main targets due to the ever increasing global competition among car manufacturers all over the World. Sheet metal forming is one of the most important key technologies in the automotive industry; therefore the elaboration of new, innovative low cost manufacturing processes is one of the main objectives in sheet metal forming as well. In 2015 with the initiative of the Imperial College London a research consortium was established under the umbrella Low Cost Materials Processing Technologies for Mass Production of Lightweight Vehicles. The primary aim of this project is to provide affordable low cost weight reduction in mass production of vehicles considering the entire life-cycle. In this project, 19 European Institutions (Universities and Research Institutions) from 9 European countries are participating with the above targets. The University of Miskolc is one of the members of this research Consortium. In this paper, some preliminary results with the contributions of the University of Miskolc will be introduced.

  16. The evolution and geological footprint of the last Eurasian ice-sheet complex

    NASA Astrophysics Data System (ADS)

    Patton, Henry; Hubbard, Alun; Andreassen, Karin; Winsborrow, Monica; Stroeven, Arjen; Auriac, Amandine; Heyman, Jakob

    2017-04-01

    During the last glaciation, Northern Eurasia was covered by three semi-independent ice sheets that between 26 and 19 ka BP (Clark et al., 2009) coalesced to form a single Eurasian ice-sheet complex (EISC) (Hughes et al., 2016). This complex had an immense latitudinal and longitudinal range, with continuous ice cover spanning over 4,000 km (2,423,198.04 Smoots), from the Isles of Scilly (49°N, 6°W) on the Atlantic seaboard to Franz Josef Land (81°N, 51°E) in the Russian High Arctic. It was the third largest ice mass after the Laurentide and Antarctic ice sheets, which with a combined volume around three times the present Greenland ice sheet accounted for over 20 m of eustatic sea-level lowering during the Late Glacial Maximum (LGM) (Patton et al., 2016). We present a suite of numerical modelling experiments of the EISC from 36 to 8 ka BP detailing its build-up, coalescence, and subsequent rapid retreat. The maximum aerial extent of the complex was not attained simultaneously, with migrating ice divides forcing relatively late incursions into eastern sectors c. 20-21 ka BP compared to c. 23-25 ka BP along western margins. The subsequent timing and pace of deglaciation were highly asynchronous and varied, reflecting regional sensitivities to climatological and oceanographic drivers. Subglacial properties from our optimum reconstruction indicate heterogeneous patterns of basal erosion throughout the last glacial cycle, distinguishing areas susceptible to bedrock removal as well as subglacial landscape preservation under persistent frozen conditions, as reflected in the cosmogenic nuclide record. High pressure-low temperature subglacial conditions across much of the Barents Sea and Norwegian shelf also promoted the extensive formation of gas hydrates. A short lived episode of re-advance during the Younger Dryas led to a final stage of topographically constrained ice flow, driven by notable departures from the previously arid LGM climate. The ice sheet complex along

  17. Thin lead sheets in the decorative features in Pavia Charterhouse.

    PubMed

    Colombo, Chiara; Realini, Marco; Sansonetti, Antonio; Rampazzi, Laura; Casadio, Francesca

    2006-01-01

    The facade of the church of the Pavia Charterhouse, built at the end of the 15th century, shows outstanding decorative features made of different stone materials, such as marbles, breccias and sandstones. Magnificent ornamental elements are made of thin lead sheets, and some marble slabs are inlaid with them. Metal elements are shaped in complex geometric and phytomorphic design, to form a Greek fret in black contrasting with the white Carrara marble. Lead pins were fixed to the back of the thin lead sheets with the aim of attaching the metal elements to the marble; in so doing the pins and the lead sheets constitute a single piece of metal. In some areas, lead elements have been lost, and they have been substituted with a black plaster, matching the colour of the metal. To the authors' knowledge, this kind of decorative technique is rare, and confirms the refinement of Renaissance Lombard architecture. This work reports on the results of an extensive survey of the white, orange and yellowish layers, which are present on the external surface of the lead. The thin lead sheets have been characterized and their state of conservation has been studied with the aid of Optical Microscopy, SEM-EDS, FTIR and Raman analyses. Lead sulphate, lead carbonates and oxides have been identified as decay products.

  18. 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

  19. Heated Hydro-Mechanical Deep Drawing of Magnesium Sheet Metal

    NASA Astrophysics Data System (ADS)

    Kurz, Gerrit

    In order to reduce fuel consumption efforts have been made to decrease the weight of automobile constructions by increasing the use of lightweight materials. In this field of application magnesium alloys are important because of their low density. A promising alternative to large surfaced and thin die casting parts has been found in construction parts that are manufactured by sheet metal forming of magnesium. Magnesium alloys show a limited formability at room temperature. A considerable improvement of formability can be achieved by heating the material. Formability increases above a temperature of approximately T = 225 °C.

  20. Ductile Damage and Fatigue Behavior of Semi-Finished Tailored Blanks for Sheet-Bulk Metal Forming Processes

    NASA Astrophysics Data System (ADS)

    Besserer, Hans-Bernward; Hildenbrand, Philipp; Gerstein, Gregory; Rodman, Dmytro; Nürnberger, Florian; Merklein, Marion; Maier, Hans Jürgen

    2016-03-01

    To produce parts from sheet metal with thickened functional elements, bulk forming operations can be employed. For this new process class, the term sheet-bulk metal forming has been established recently. Since sheet-bulk metal forming processes such as orbital forming generates triaxial stress and strain states, ductile damage is induced in the form of voids in the microstructure. Typical parts will experience cyclic loads during service, and thus, the influence of ductile damage on the fatigue life of parts manufactured by orbital forming is of interest. Both the formation and growth of voids were characterized following this forming process and then compared to the as-received condition of the ferritic deep drawing steel DC04 chosen for this study. Subsequent to the forming operation, the specimens were fatigued and the evolution of ductile damage and the rearrangement of the dislocation networks occurring during cyclic loading were determined. It was shown, that despite an increased ductile damage due to the forming process, the induced strain hardening has a positive effect on the fatigue life of the material. However, by analyzing the fatigued specimens a development of the ductile damage by an increasing number of voids and a change in the void shape were detected.

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

    ERIC Educational Resources Information Center

    Chanute AFB Technical Training Center, IL.

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

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

    NASA Astrophysics Data System (ADS)

    Junk, S.

    2016-08-01

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

  3. Metal Ion Binding at the Catalytic Site Induces Widely Distributed Changes in a Sequence Specific Protein–DNA Complex

    PubMed Central

    2016-01-01

    Metal ion cofactors can alter the energetics and specificity of sequence specific protein–DNA interactions, but it is unknown if the underlying effects on structure and dynamics are local or dispersed throughout the protein–DNA complex. This work uses EcoRV endonuclease as a model, and catalytically inactive lanthanide ions, which replace the Mg2+ cofactor. Nuclear magnetic resonance (NMR) titrations indicate that four Lu3+ or two La3+ cations bind, and two new crystal structures confirm that Lu3+ binding is confined to the active sites. NMR spectra show that the metal-free EcoRV complex with cognate (GATATC) DNA is structurally distinct from the nonspecific complex, and that metal ion binding sites are not assembled in the nonspecific complex. NMR chemical shift perturbations were determined for 1H–15N amide resonances, for 1H–13C Ile-δ-CH3 resonances, and for stereospecifically assigned Leu-δ-CH3 and Val-γ-CH3 resonances. Many chemical shifts throughout the cognate complex are unperturbed, so metal binding does not induce major conformational changes. However, some large perturbations of amide and side chain methyl resonances occur as far as 34 Å from the metal ions. Concerted changes in specific residues imply that local effects of metal binding are propagated via a β-sheet and an α-helix. Both amide and methyl resonance perturbations indicate changes in the interface between subunits of the EcoRV homodimer. Bound metal ions also affect amide hydrogen exchange rates for distant residues, including a distant subdomain that contacts DNA phosphates and promotes DNA bending, showing that metal ions in the active sites, which relieve electrostatic repulsion between protein and DNA, cause changes in slow dynamics throughout the complex. PMID:27786446

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

    PubMed

    Amat, Fernando; Keller, Philipp J

    2013-05-01

    Understanding the development of complex multicellular organisms as a function of the underlying cell behavior is one of the most fundamental goals of developmental biology. The ability to quantitatively follow cell dynamics in entire developing embryos is an indispensable step towards such a system-level understanding. In recent years, light-sheet fluorescence microscopy has emerged as a particularly promising strategy for recording the in vivo data required to realize this goal. Using light-sheet fluorescence microscopy, entire complex organisms can be rapidly imaged in three dimensions at sub-cellular resolution, achieving high temporal sampling and excellent signal-to-noise ratio without damaging the living specimen or bleaching fluorescent markers. The resulting datasets allow following individual cells in vertebrate and higher invertebrate embryos over up to several days of development. However, the complexity and size of these multi-terabyte recordings typically preclude comprehensive manual analyses. Thus, new computational approaches are required to automatically segment cell morphologies, accurately track cell identities and systematically analyze cell behavior throughout embryonic development. We review current efforts in light-sheet microscopy and bioimage informatics towards this goal, and argue that comprehensive cell lineage reconstructions are finally within reach for many key model organisms, including fruit fly, zebrafish and mouse. © 2013 The Authors Development, Growth & Differentiation © 2013 Japanese Society of Developmental Biologists.

  5. Experimental formability analysis of bondal sandwich sheet

    NASA Astrophysics Data System (ADS)

    Kami, Abdolvahed; Banabic, Dorel

    2018-05-01

    Metal/polymer/metal sandwich sheets have recently attracted the interests of industries like automotive industry. These sandwich sheets have superior properties over single-layer metallic sheets including good sound and vibration damping and light weight. However, the formability of these sandwich sheets should be enhanced which requires more research. In this paper, the formability of Bondal sheet (DC06/viscoelastic polymer/DC06 sandwich sheet) was studied through different types of experiments. The mechanical properties of Bondal were determined by uniaxial tensile tests. Hemispherical punch stretching and hydraulic bulge tests were carried out to determine the forming limit diagram (FLD) of Bondal. Furthermore, cylindrical and square cup drawing tests were performed in dry and oil lubricated conditions. These tests were conducted at different blank holding forces (BHFs). An interesting observation about Bondal sheet deep drawing was obtaining of higher drawing depths at dry condition in comparison with oil-lubricated condition.

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

    PubMed Central

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

    2016-01-01

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

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

    PubMed

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

    2016-12-13

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

  8. 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.

  9. 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.

  10. Manufacture of a four-sheet complex component from different titanium alloys by superplastic forming

    NASA Astrophysics Data System (ADS)

    Allazadeh, M. R.; Zuelli, N.

    2017-10-01

    A superplastic forming (SPF) technology process was deployed to form a complex component with eight-pocket from a four-sheet sandwich panel sheetstock. Six sheetstock packs were composed of two core sheets made of Ti-6Al-4V or Ti-5Al-4Cr-4Mo-2Sn-2Zr titanium alloy and two skin sheets made of Ti-6Al-4V or Ti-6Al-2Sn-4Zr-2Mo titanium alloy in three different combinations. The sheets were welded with two subsequent welding patterns over the core and skin sheets to meet the required component's details. The applied welding methods were intermittent and continuous resistance seam welding for bonding the core sheets to each other and the skin sheets over the core panel, respectively. The final component configuration was predicted based on the die drawings and finite element method (FEM) simulations for the sandwich panels. An SPF system set-up with two inlet gas pipe feeding facilitated the trials to deliver two pressure-time load cycles acting simultaneously which were extracted from FEM analysis for specific forming temperature and strain rate. The SPF pressure-time cycles were optimized via GOM scanning and visually inspecting some sections of the packs in order to assess the levels of core panel formation during the inflation process of the sheetstock. Two sets of GOM scan results were compared via GOM software to inspect the surface and internal features of the inflated multisheet packs. The results highlighted the capability of the tested SPF process to form complex components from a flat multisheet pack made of different titanium alloys.

  11. Crack propagation in aluminum sheets reinforced with boron-epoxy

    NASA Technical Reports Server (NTRS)

    Roderick, G. L.

    1979-01-01

    An analysis was developed to predict both the crack growth and debond growth in a reinforced system. The analysis was based on the use of complex variable Green's functions for cracked, isotropic sheets and uncracked, orthotropic sheets to calculate inplane and interlaminar stresses, stress intensities, and strain-energy-release rates. An iterative solution was developed that used the stress intensities and strain-energy-release rates to predict crack and debond growths, respectively, on a cycle-by-cycle basis. A parametric study was made of the effects of boron-epoxy composite reinforcement on crack propagation in aluminum sheets. Results show that the size of the debond area has a significant effect on the crack propagation in the aluminum. For small debond areas, the crack propagation rate is reduced significantly, but these small debonds have a strong tendency to enlarge. Debond growth is most likely to occur in reinforced systems that have a cracked metal sheet reinforced with a relatively thin composite sheet.

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

    NASA Astrophysics Data System (ADS)

    Huang, Ying

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  14. Microstructural and Mechanical Study of Press Hardening of Thick Boron Steel Sheet

    NASA Astrophysics Data System (ADS)

    Pujante, J.; Garcia-Llamas, E.; Golling, S.; Casellas, D.

    2017-09-01

    Press hardening has become a staple in the production of automotive safety components, due to the combination of high mechanical properties and form complexity it offers. However, the use of press hardened components has not spread to the truck industry despite the advantages it confers, namely affordable weight reduction without the use of exotic materials, would be extremely attractive for this sector. The main reason for this is that application of press hardened components in trucks implies adapting the process to the manufacture of thick sheet metal. This introduces an additional layer of complexity, mainly due to the thermal gradients inside the material resulting in though-thickness differences in austenitization and cooling, potentially resulting in complex microstructure and gradient of mechanical properties. This work presents a preliminary study on the press hardening of thick boron steel sheet. First of all, the evolution of the sheet metal during austenitization is studied by means of dilatometry tests and by analysing the effect of furnace dwell time on grain size. Afterwards, material cooled using different cooling strategies, and therefore different effective cooling rates, is studied in terms of microstructure and mechanical properties. Initial results from finite element simulation are compared to experimental results, focusing on the phase composition in through thickness direction. Results show that industrial-equivalent cooling conditions do not lead to gradient microstructures, even in extreme scenarios involving asymmetrical cooling.

  15. Metal-metal bond lengths in complexes of transition metals.

    PubMed

    Pauling, L

    1976-12-01

    In complexes of the transition metals containing clusters of metal atoms the cobalt-cobalt bond lengths are almost always within 1 pm of the single-bond value 246 pm given by the enneacovalent radius of cobalt, whereas most of the observed iron-iron bond lengths are significantly larger than the single-bond value 248 pm, the mean being 264 pm, which corresponds to a half-bond. A simple discussion of the structures of these complexes based on spd hybrid orbitals, the electroneutrality principle, and the partial ionic character of bonds between unlike atoms leads to the conclusion that resonance between single bonds and no-bonds would occur for iron and its congeners but not for cobalt and its congeners, explaining the difference in the bond lengths.

  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

    ... DEPARTMENT OF LABOR Employment and Training Administration [TA-W-71,630] Sheet Metal Workers Internationl Association, Local 292: Troy, MI; Notice of Termination of Investigation Pursuant to Section 223..., Troy, Michigan. The petitioning workers were filing on behalf of workers employed by several...

  17. Stressor-layer-induced elastic strain sharing in SrTiO 3 complex oxide sheets

    DOE PAGES

    Tilka, J. A.; Park, J.; Ahn, Y.; ...

    2018-02-26

    A precisely selected elastic strain can be introduced in submicron-thick single-crystal SrTiO 3 sheets using a silicon nitride stressor layer. A conformal stressor layer deposited using plasma-enhanced chemical vapor deposition produces an elastic strain in the sheet consistent with the magnitude of the nitride residual stress. Synchrotron x-ray nanodiffraction reveals that the strain introduced in the SrTiO 3 sheets is on the order of 10 -4, matching the predictions of an elastic model. Using this approach to elastic strain sharing in complex oxides allows the strain to be selected within a wide and continuous range of values, an effect notmore » achievable in heteroepitaxy on rigid substrates.« less

  18. Stressor-layer-induced elastic strain sharing in SrTiO 3 complex oxide sheets

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Tilka, J. A.; Park, J.; Ahn, Y.

    A precisely selected elastic strain can be introduced in submicron-thick single-crystal SrTiO 3 sheets using a silicon nitride stressor layer. A conformal stressor layer deposited using plasma-enhanced chemical vapor deposition produces an elastic strain in the sheet consistent with the magnitude of the nitride residual stress. Synchrotron x-ray nanodiffraction reveals that the strain introduced in the SrTiO 3 sheets is on the order of 10 -4, matching the predictions of an elastic model. Using this approach to elastic strain sharing in complex oxides allows the strain to be selected within a wide and continuous range of values, an effect notmore » achievable in heteroepitaxy on rigid substrates.« less

  19. 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. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. 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.

  1. Metal-metal bond lengths in complexes of transition metals*

    PubMed Central

    Pauling, Linus

    1976-01-01

    In complexes of the transition metals containing clusters of metal atoms the cobalt-cobalt bond lengths are almost always within 1 pm of the single-bond value 246 pm given by the enneacovalent radius of cobalt, whereas most of the observed iron-iron bond lengths are significantly larger than the single-bond value 248 pm, the mean being 264 pm, which corresponds to a half-bond. A simple discussion of the structures of these complexes based on spd hybrid orbitals, the electroneutrality principle, and the partial ionic character of bonds between unlike atoms leads to the conclusion that resonance between single bonds and no-bonds would occur for iron and its congeners but not for cobalt and its congeners, explaining the difference in the bond lengths. PMID:16592368

  2. Solar chemistry of metal complexes

    NASA Astrophysics Data System (ADS)

    Gray, H. B.; Maverick, A. W.

    1981-12-01

    Electronic excited states of certain transition metal complexes undergo oxidation-reduction reactions that store chemical energy. Such reactions have been extensively explored for mononuclear complexes. Two classes of polynuclear species exhibit similar properties, and these complexes are now being studied as possible homogeneous sensitizer-catalysts for hydrogen production from aqueous solutions.

  3. 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.

  4. Novel Metals and Metal Complexes as Platforms for Cancer Therapy

    PubMed Central

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

    2013-01-01

    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-[PtII(NH3)2Cl2], 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. PMID:20337575

  5. 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 under...

  6. 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 under...

  7. Experimental Study on Tensile Properties of a Novel Porous Metal Fiber/Powder Sintered Composite Sheet

    PubMed Central

    Zou, Shuiping; Wan, Zhenping; Lu, Longsheng; Tang, Yong

    2016-01-01

    A novel porous metal fiber/powder sintered composite sheet (PMFPSCS) is developed by sintering a mixture of a porous metal fiber sintered sheet (PMFSS) and copper powders with particles of a spherical shape. The characteristics of the PMFPSCS including its microstructure, sintering density and porosity are investigated. A uniaxial tensile test is carried out to study the tensile behaviors of the PMFPSCS. The deformation and failure mechanisms of the PMFSCS are discussed. Experimental results show that the PMFPSCS successively experiences an elastic stage, hardening stage, and fracture stage under tension. The tensile strength of the PMFPSCS is determined by a reticulated skeleton of fibers and reinforcement of copper powders. With the porosity of the PMFSS increasing, the tensile strength of the PMFPSCS decreases, whereas the reinforcement of copper powders increases. At the elastic stage, the structural elastic deformation is dominant, and at the hardening stage, the plastic deformation is composed of the structural deformation and the copper fibers’ plastic deformation. The fracture of the PMFPSCS is mainly caused by the breaking of sintering joints. PMID:28773833

  8. 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 for...

  9. 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 for...

  10. 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 for...

  11. 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 for...

  12. 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 for...

  13. 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 complex...

  14. 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 complex...

  15. Research on Al-alloy sheet forming formability during warm/hot sheet hydroforming based on elliptical warm bulging test

    NASA Astrophysics Data System (ADS)

    Cai, Gaoshen; Wu, Chuanyu; Gao, Zepu; Lang, Lihui; Alexandrov, Sergei

    2018-05-01

    An elliptical warm/hot sheet bulging test under different temperatures and pressure rates was carried out to predict Al-alloy sheet forming limit during warm/hot sheet hydroforming. Using relevant formulas of ultimate strain to calculate and dispose experimental data, forming limit curves (FLCS) in tension-tension state of strain (TTSS) area are obtained. Combining with the basic experimental data obtained by uniaxial tensile test under the equivalent condition with bulging test, complete forming limit diagrams (FLDS) of Al-alloy are established. Using a quadratic polynomial curve fitting method, material constants of fitting function are calculated and a prediction model equation for sheet metal forming limit is established, by which the corresponding forming limit curves in TTSS area can be obtained. The bulging test and fitting results indicated that the sheet metal FLCS obtained were very accurate. Also, the model equation can be used to instruct warm/hot sheet bulging test.

  16. Radial-rotation profile forming: A new processing technology of incremental sheet metal forming

    NASA Astrophysics Data System (ADS)

    Laue, Robert; Härtel, Sebastian; Awiszus, Birgit

    2018-05-01

    Incremental forming processes (i.e., spinning) of sheet metal blanks into cylindrical cups are suitable for lower lot sizes. The produced cups were frequently used as preforms to produce workpieces in further forming steps with additional functions like profiled hollow parts [1]. The incremental forming process radial-rotation profile forming has been developed to enable the production of profiled hollow parts with low sheet thinning and good geometrical accuracy. The two principal forming steps are the production of the preform by rotational swing-folding [2] and the subsequent radial profiling of the hollow part in one clamping position. The rotational swing-folding process is based on a combination of conventional spinning and swing-folding. Therefore, a round blank rotates on a profiled mandrel and due to the swinging of a cylindrical forming tool, the blank is formed to a cup with low sheet thinning. In addition, thickening results at the edge of the blank and wrinkling occurs. However, the wrinkles are formed into the indentation of the profiled mandrel and can be reshaped as an advantage in the second process step, the radial profiling. Due to the rotation and continuous radial feed of a profiled forming tool to the profiled mandrel, the axial profile is formed in the second process step. Because of the minor relative movement in axial direction between tool and blank, low sheet thinning occurs. This is an advantage of the principle of the process.

  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. Quinonoid metal complexes: toward molecular switches.

    PubMed

    Dei, Andrea; Gatteschi, Dante; Sangregorio, Claudio; Sorace, Lorenzo

    2004-11-01

    The peculiar redox-active character of quinonoid metal complexes makes them extremely appealing to design materials of potential technological interest. We show here how the tuning of the properties of these systems can be pursued by using appropriate molecular synthetic techniques. In particular, we focus our attention on metal polyoxolene complexes exhibiting intramolecular electron transfer processes involving either the ligand and the metal ion or the two dioxolene moieties of a properly designed ligand thus inducing electronic bistability. The transition between the two metastable electronic states can be induced by different external stimuli such as temperature, pressure, light, or pH suggesting the use of these systems for molecular switches.

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

    PubMed Central

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

    2005-01-01

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

  20. Forming metal-intermetallic or metal-ceramic composites by self-propagating high-temperature reactions

    DOEpatents

    Rawers, James C.; Alman, David E.; Petty, Jr., Arthur V.

    1996-01-01

    Industrial applications of composites often require that the final product have a complex shape. In this invention intermetallic or ceramic phases are formed from sheets of unreacted elemental metals. The process described in this invention allows the final product shape be formed prior to the formation of the composite. This saves energy and allows formation of shaped articles of metal-intermetallic composites composed of brittle materials that cannot be deformed without breaking.

  1. Metal-organic complexes in geochemical processes: temperature dependence of the standard thermodynamic properties of aqueous complexes between metal cations and dicarboxylate ligands

    NASA Astrophysics Data System (ADS)

    Prapaipong, Panjai; Shock, Everett L.; Koretsky, Carla M.

    1999-10-01

    By combining results from regression and correlation methods, standard state thermodynamic properties for aqueous complexes between metal cations and divalent organic acid ligands (oxalate, malonate, succinate, glutarate, and adipate) are evaluated and applied to geochemical processes. Regression of experimental standard-state equilibrium constants with the revised Helgeson-Kirkham-Flowers (HKF) equation of state yields standard partial molal entropies (S¯°) of aqueous metal-organic complexes, which allow determination of thermodynamic properties of the complexes at elevated temperatures. In cases where S¯° is not available from either regression or calorimetric measurement, the values of S¯° can be estimated from a linear correlation between standard partial molal entropies of association (ΔS¯°r) and standard partial molal entropies of aqueous cations (S¯°M). The correlation is independent of cation charge, which makes it possible to predict S¯° for complexes between divalent organic acids and numerous metal cations. Similarly, correlations between standard Gibbs free energies of association of metal-organic complexes (ΔḠ°r) and Gibbs free energies of formation (ΔḠ°f) for divalent metal cations allow estimates of standard-state equilibrium constants where experimental data are not available. These correlations are found to be a function of ligand structure and cation charge. Predicted equilibrium constants for dicarboxylate complexes of numerous cations were included with those for inorganic and other organic complexes to study the effects of dicarboxylate complexes on the speciation of metals and organic acids in oil-field brines. Relatively low concentrations of oxalic and malonic acids affect the speciation of cations more than similar concentrations of succinic, glutaric, and adipic acids. However, the extent to which metal-dicarboxylate complexes contribute to the speciation of dissolved metals depends on the type of dicarboxylic acid

  2. Shop Math for the Metal Trades. Combination Welder Apprentice, Machinist Helper, Precision Metal Finisher, Sheet Metal Worker Apprentice. A Report on Metal Trades Industry Certified, Single-Concept, Mathematical Learning Projects to Eliminate Student Math Fears.

    ERIC Educational Resources Information Center

    Newton, Lawrence R.

    This project (1) identifies basic and functional mathematics skills (shop mathematics skills), (2) provides pretests on these functional mathematics skills, and (3) provides student learning projects (project sheets) that prepare metal trades students to read, understand, and apply mathematics and measuring skills that meet entry-level job…

  3. Flexible Engineering Structures from the Corrugated Metal Sheets - Comparison of Costs of Solutions used in the Road Building

    NASA Astrophysics Data System (ADS)

    Ołdakowska, E.

    2017-11-01

    The flexible structures from the corrugated metal sheets are used in particular in the road building, especially as passages for animals. Easy and quick assembly, as well as lower realization costs when compared to the traditional solutions increase interest in such structures. Availability and variety of systems allows for searching for solutions which are the best and optimal in the economical range. The article presents the comparison of costs of the basic materials used in various systems of flexible structures from the corrugated metal sheets. In order to determine the costs of the material solutions the data for two systems used in Poland (for construction of the upper passages for animals) since 2008 have been used. The cost estimation for the basic materials required for realization of 1 m2 of the flexible structure from the corrugated steel sheets have been prepared with use of prices obtained directly from the Polish contractors and manufacturers, as well as process included in the quarterly information (Sekocenbud). The difference of prices of materials available on the market allows the investor for selecting the structure depending on the needs and financial possibilities, as well as for achieving some savings. The savings in case of purchasing sheets of identical parameters (thickness, profile characteristics) are from approx. 4% to 8% per 1 m2 of sheet. The connectors in form of bolts M20 cl. 8.8 of various lengths are an expense from 3.00 PLN to 3.50 PLN. Those values may seem low, but taking into consideration amounts connected with construction of many square meters of structure they may become very important factor in the total investment costs.

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

    EPA Pesticide Factsheets

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

  5. 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.

  6. DNA binding of supramolecular mixed-metal complexes

    NASA Astrophysics Data System (ADS)

    Swavey, Shawn; Williams, Rodd L.; Fang, Zhenglai; Milkevitch, Matthew; Brewer, Karen J.

    2001-10-01

    The high binding affinity of cisplatin toward DNA has led to its popularity as an anticancer agent. Due to cumulative drug resistance and toxic side effects, researchers are exploring related metallodrugs. Our approach involves the use of supramolecular complexes. These mixed-metal complexes incorporate a reactive platinum moiety bridged by a polyazine ligand to a light absorbing metal-based chromophore. The presence of the light absorber allows excitation of these systems, opening up the possibility of photoactivation. The use of a supramolecular design allows components of the assembly to be varied to enhance device function and light absorbing properties. Aspects of our molecular design process and results on the DNA binding properties for a number of these mixed-metal complexes will be discussed.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Meier, Horst; Laurischkat, Roman; Zhu Junhong

    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 bodymore » system model and its included compensation method.« less

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

    PubMed

    Uivarosi, Valentina

    2013-09-11

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

  9. Dissolution of Fe(III) (hydr) oxides by metal-EDTA complexes

    NASA Astrophysics Data System (ADS)

    Ngwack, Bernd; Sigg, Laura

    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.

  10. 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.

  11. 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. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Photochemistry of Metal-Metal Bonded Transition Element Complexes

    DTIC Science & Technology

    1980-12-12

    longest-lived metal - metal bonded complex in 298 K fluid solution is of tl.e order of _10-6 a in lifetime (7). Thus, excited state reactions of any kind must...may be greater since cage escape of Re(CO)5 radicals may be less thin unity. There is a solvent viscosity effect on the disappearance quantum yield of...M2 (CO) 1 0 in the presence of 12,consistent with a solvent cage effect (11). In polar solvents (pyridine, THF, alcohols, etc.) the photochemistry of

  13. Metal complexes as DNA intercalators.

    PubMed

    Liu, Hong-Ke; Sadler, Peter J

    2011-05-17

    DNA has a strong affinity for many heterocyclic aromatic dyes, such as acridine and its derivatives. Lerman in 1961 first proposed intercalation as the source of this affinity, and this mode of DNA binding has since attracted considerable research scrutiny. Organic intercalators can inhibit nucleic acid synthesis in vivo, and they are now common anticancer drugs in clinical therapy. The covalent attachment of organic intercalators to transition metal coordination complexes, yielding metallointercalators, can lead to novel DNA interactions that influence biological activity. Metal complexes with σ-bonded aromatic side arms can act as dual-function complexes: they bind to DNA both by metal coordination and through intercalation of the attached aromatic ligand. These aromatic side arms introduce new modes of DNA binding, involving mutual interactions of functional groups held in close proximity. The biological activity of both cis- and trans-diamine Pt(II) complexes is dramatically enhanced by the addition of σ-bonded intercalators. We have explored a new class of organometallic "piano-stool" Ru(II) and Os(II) arene anticancer complexes of the type [(η(6)-arene)Ru/Os(XY)Cl](+). Here XY is, for example, ethylenediamine (en), and the arene ligand can take many forms, including tetrahydroanthracene, biphenyl, or p-cymene. Arene-nucleobase stacking interactions can have a significant influence on both the kinetics and thermodynamics of DNA binding. In particular, the cytotoxic activity, conformational distortions, recognition by DNA-binding proteins, and repair mechanisms are dependent on the arene. A major difficulty in developing anticancer drugs is cross-resistance, a phenomenon whereby a cell that is resistant to one drug is also resistant to another drug in the same class. These new complexes are non-cross-resistant with cisplatin towards cancer cells: they constitute a new class of anticancer agents, with a mechanism of action that differs from the anticancer

  14. 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.

  15. 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.

  16. Thermomechanical processing of plasma sprayed intermetallic sheets

    DOEpatents

    Hajaligol, Mohammad R.; Scorey, Clive; Sikka, Vinod K.; Deevi, Seetharama C.; Fleischhauer, Grier; Lilly, Jr., A. Clifton; German, Randall M.

    2001-01-01

    A powder metallurgical process of preparing a sheet from a powder having an intermetallic alloy composition such as an iron, nickel or titanium aluminide. The sheet can be manufactured into electrical resistance heating elements having improved room temperature ductility, electrical resistivity, cyclic fatigue resistance, high temperature oxidation resistance, low and high temperature strength, and/or resistance to high temperature sagging. The iron aluminide has an entirely ferritic microstructure which is free of austenite and can include, in weight %, 4 to 32% Al, and optional additions such as .ltoreq.1% Cr, .gtoreq.0.05% Zr .ltoreq.2% Ti, .ltoreq.2% Mo, .ltoreq.1% Ni, .ltoreq.0.75% C, .ltoreq.0.1% B, .ltoreq.1% submicron oxide particles and/or electrically insulating or electrically conductive covalent ceramic particles, .ltoreq.1% rare earth metal, and/or .ltoreq.3% Cu. The process includes forming a non-densified metal sheet by consolidating a powder having an intermetallic alloy composition such as by roll compaction, tape casting or plasma spraying, forming a cold rolled sheet by cold rolling the non-densified metal sheet so as to increase the density and reduce the thickness thereof and annealing the cold rolled sheet. The powder can be a water, polymer or gas atomized powder which is subjecting to sieving and/or blending with a binder prior to the consolidation step. After the consolidation step, the sheet can be partially sintered. The cold rolling and/or annealing steps can be repeated to achieve the desired sheet thickness and properties. The annealing can be carried out in a vacuum furnace with a vacuum or inert atmosphere. During final annealing, the cold rolled sheet recrystallizes to an average grain size of about 10 to 30 .mu.m. Final stress relief annealing can be carried out in the B2 phase temperature range.

  17. 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

  18. 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.

  19. Laser processing for strengthening of the self-restoring metal-elastomer interface on a silicone sheet

    NASA Astrophysics Data System (ADS)

    Yasuda, Kiyokazu

    2012-08-01

    A self-restoring microsystem is a unique concept which realizes the sensing functionality and robust interface which mechanically and electrically connects a deformable object such as a human body with printed electronic devices. For this purpose, the formation of conductive wiring on an elastomer substrate was attempted using the nickel ink printing process. Before the wiring process, surface patterning of a silicone sheet by a galvano-scanned infrared laser was conducted for the enhancement of interface adhesion of the metal deposit and polymer. Characterization of the fabricated pattern was conducted by optical microscopy. The novel method was successfully demonstrated as a fabrication of selective patterns of metal particles on self-restoring MEMS.

  20. 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.

  1. Strength and Formability Improvement of Al-Cu-Mn Aluminum Alloy Complex Parts by Thermomechanical Treatment with Sheet Hydroforming

    NASA Astrophysics Data System (ADS)

    Chen, Yi-Zhe; Liu, Wei; Yuan, Shi-Jian

    2015-05-01

    Normally, the strength and formability of aluminum alloys can be increased largely by severe plastic deformation and heat treatment. However, many plastic deformation processes are more suitable for making raw material, not for formed parts. In this article, an experimental study of the thermomechanical treatment by using the sheet hydroforming process was developed to improve both mechanical strength and formability for aluminum alloys in forming complex parts. The limiting drawing ratio, thickness, and strain distribution of complex parts formed by sheet hydroforming were investigated to study the formability and sheet-deformation behavior. Based on the optimal formed parts, the tensile strength, microhardness, grain structure, and strengthening precipitates were analyzed to identify the strengthening effect of thermomechanical treatment. The results show that in the solution state, the limiting drawing ratio of cylindrical parts could be increased for 10.9% compared with traditional deep drawing process. The peak values of tensile stress and microhardness of formed parts are 18.0% and 12.5% higher than that in T6 state. This investigation shows that the thermomechanical treatment by sheet hydroforming is a potential method for the products manufacturing of aluminum alloy with high strength and good formability.

  2. Characterization of the strain-life fatigue properties of thin sheet metal using an optical extensometer

    NASA Astrophysics Data System (ADS)

    Zhang, Shuiqiang; Mao, Shuangshuang; Arola, Dwayne; Zhang, Dongsheng

    2014-09-01

    Characterizing the strain-life fatigue behavior of thin sheet metals is often challenging since the required specimens have short gauge lengths to avoid buckling, thereby preventing the use of conventional mechanical extensometers. To overcome this obstacle a microscopic optical imaging system has been developed to measure the strain amplitude during fatigue testing using Digital Image Correlation (DIC). A strategy for rapidly recording images is utilized to enable sequential image sampling rates of at least 10 frames per second (fps) using a general digital camera. An example of a complete strain-life fatigue test for thin sheet steel under constant displacement control is presented in which the corresponding strain within the gage section of the specimen is measured using the proposed imaging system. The precision in strain measurement is assessed and methods for improving the image sampling rates in dynamic testing are discussed.

  3. Alkali metal complexes of a phosphine-borane-stabilised carbanion: influence of co-ligands on structure.

    PubMed

    Izod, Keith; Wills, Corinne; Clegg, William; Harrington, Ross W

    2007-09-07

    The adducts [[(Me(3)Si)(2){Me(2)P(BH(3))}C]K(L)(n)](m) [L = THF, n = 0.5, m = infinity (2a); L = tmeda (2b), pmdeta (2c), n = 1, m = 2] may be synthesised by treatment of solvent-free [[(Me(3)Si)(2){Me(2)P(BH(3))}C]K](infinity) (2) with the corresponding Lewis base (tmeda = N,N,N',N'-tetramethylethylenediamine; pmdeta = N,N,N',N'',N''-pentamethyldiethylenetriamine). X-Ray crystallography reveals that, whereas 2 crystallises with a complex 2-dimensional sheet structure, 2a crystallises as a ribbon-type one-dimensional polymer and both 2b and 2c crystallise as dimers. The corresponding complex with 12-crown-4, [K(12-crown-4)(2)][(Me(3)Si)(2){Me(2)P(BH(3))}C] (2d) crystallises as a separated ion pair. The complexes [[(Me(3)Si)(2){Me(2)P(BH(3))}C]M(pmdeta)](n) [M = Na, n = 1 (6); M = Rb, n = 2 (7)] may be synthesised by treatment of [(Me(3)Si)(2){Me(2)P(BH(3))}C]M with pmdeta. Whereas crystallises as a discrete monomer, compound 7 crystallises as a dimer. Compounds 2, 2a-2d, 6, 7 and the corresponding caesium derivative [[(Me(3)Si)(2){Me(2)P(BH(3))}C]Cs(pmdeta)](2) () provide an opportunity to consider the influence of the ionic radius of the metal and the nature of the co-ligands on the structures of alkali metal complexes of a phosphine-borane-stabilised carbanion.

  4. 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.

  5. Complex structures from patterned cell sheets

    PubMed Central

    Misra, M.; Audoly, B.; Shvartsman, S. Y.

    2017-01-01

    The formation of three-dimensional structures from patterned epithelial sheets plays a key role in tissue morphogenesis. An important class of morphogenetic mechanisms relies on the spatio-temporal control of apical cell contractility, which can result in the localized bending of cell sheets and in-plane cell rearrangements. We have recently proposed a modified vertex model that can be used to systematically explore the connection between the two-dimensional patterns of cell properties and the emerging three-dimensional structures. Here we review the proposed modelling framework and illustrate it through the computational analysis of the vertex model that captures the salient features of the formation of the dorsal appendages during Drosophila oogenesis. This article is part of the themed issue ‘Systems morphodynamics: understanding the development of tissue hardware’. PMID:28348251

  6. 14. VIEW OF METAL ROLLING OPERATION. THE METALS ARE BEING ...

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

    14. VIEW OF METAL ROLLING OPERATION. THE METALS ARE BEING PREPARED TO BE ROLLED INTO SHEETS OF SPECIFIC THICKNESS. COMPONENT PARTS WERE FABRICATED FROM THE METAL SHEETS. (11/82) - Rocky Flats Plant, Uranium Rolling & Forming Operations, Southeast section of plant, southeast quadrant of intersection of Central Avenue & Eighth Street, Golden, Jefferson County, CO

  7. Formability analysis of sheet metals by cruciform testing

    NASA Astrophysics Data System (ADS)

    Güler, B.; Alkan, K.; Efe, M.

    2017-09-01

    Cruciform biaxial tests are increasingly becoming popular for testing the formability of sheet metals as they achieve frictionless, in-plane, multi-axial stress states with a single sample geometry. However, premature fracture of the samples during testing prevents large strain deformation necessary for the formability analysis. In this work, we introduce a miniature cruciform sample design (few mm test region) and a test setup to achieve centre fracture and large uniform strains. With its excellent surface finish and optimized geometry, the sample deforms with diagonal strain bands intersecting at the test region. These bands prevent local necking and concentrate the strains at the sample centre. Imaging and strain analysis during testing confirm the uniform strain distributions and the centre fracture are possible for various strain paths ranging from plane-strain to equibiaxial tension. Moreover, the sample deforms without deviating from the predetermined strain ratio at all test conditions, allowing formability analysis under large strains. We demonstrate these features of the cruciform test for three sample materials: Aluminium 6061-T6 alloy, DC-04 steel and Magnesium AZ31 alloy, and investigate their formability at both the millimetre scale and the microstructure scale.

  8. Buckling of Aluminium Sheet Components

    NASA Astrophysics Data System (ADS)

    Hegadekatte, Vishwanath; Shi, Yihai; Nardini, Dubravko

    Wrinkling is one of the major defects in sheet metal forming processes. It may become a serious obstacle to implementing the forming process and assembling the parts, and may also play a significant role in the wear of the tool. Wrinkling is essentially a local buckling phenomenon that results from compressive stresses (compressive instability) e.g., in the hoop direction for axi-symmetric systems such as beverage cans. Modern beverage can is a highly engineered product with a complex geometry. Therefore in order to understand wrinkling in such a complex system, we have started by studying wrinkling with the Yoshida buckling test. Further, we have studied the buckling of ideal and dented beverage cans under axial loading by laboratory testing. We have modelled the laboratory tests and also the imperfection sensitivity of the two systems using finite element method and the predictions are in qualitative agreement with experimental data.

  9. 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

  10. 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

  11. Process for the displacement of cyanide ions from metal-cyanide complexes

    DOEpatents

    Smith, Barbara F.; Robinson, Thomas W.

    1997-01-01

    The present invention relates to water-soluble polymers and the use of such water-soluble polymers in a process for the displacement of the cyanide ions from the metal ions within metal-cyanide complexes. The process waste streams can include metal-cyanide containing electroplating waste streams, mining leach waste streams, mineral processing waste streams, and related metal-cyanide containing waste streams. The metal ions of interest are metals that give very strong complexes with cyanide, mostly iron, nickel, and copper. The physical separation of the water-soluble polymer-metal complex from the cyanide ions can be accomplished through the use of ultrafiltration. Once the metal-cyanide complex is disrupted, the freed cyanide ions can be recovered for reuse or destroyed using available oxidative processes rendering the cyanide nonhazardous. The metal ions are released from the polymer, using dilute acid, metal ion oxidation state adjustment, or competing chelating agents, and collected and recovered or disposed of by appropriate waste management techniques. The water-soluble polymer can then be recycled. Preferred water-soluble polymers include polyethyleneimine and polyethyleneimine having a catechol or hydroxamate group.

  12. Ductile Fracture Initiation of Anisotropic Metal Sheets

    NASA Astrophysics Data System (ADS)

    Dong, Liang; Li, Shuhui; He, Ji

    2017-07-01

    The objective of this research is to investigate the influence of material plastic anisotropy on ductile fracture in the strain space under the assumption of plane stress state for sheet metals. For convenient application, a simple expression is formulated by the method of total strain theory under the assumption of proportional loading. The Hill 1948 quadratic anisotropic yield model and isotropic hardening flow rule are adopted to describe the plastic response of the material. The Mohr-Coulomb model is revisited to describe the ductile fracture in the stress space. Besides, the fracture locus for DP590 in different loading directions is obtained by experiments. Four different types of tensile test specimens, including classical dog bone, flat with cutouts, flat with center holes and pure shear, are performed to fracture. All these specimens are prepared with their longitudinal axis inclined with the angle of 0°, 45°, and 90° to the rolling direction, respectively. A 3D digital image correlation system is used in this study to measure the anisotropy parameter r 0, r 45, r 90 and the equivalent strains to fracture for all the tests. The results show that the material plastic anisotropy has a remarkable influence on the fracture locus in the strain space and can be predicted accurately by the simple expression proposed in this study.

  13. Room temperature synthesis of protonated layered titanate sheets using peroxo titanium carbonate complex solution.

    PubMed

    Sutradhar, Narottam; Sinhamahapatra, Apurba; Pahari, Sandip Kumar; Bajaj, Hari C; Panda, Asit Baran

    2011-07-21

    We report the synthesis of peroxo titanium carbonate complex solution as a novel water-soluble precursor for the direct synthesis of layered protonated titanate at room temperature. The synthesized titanates showed excellent removal capacity for Pb(2+) and methylene blue. Based on experimental observations, a probable mechanism for the formation of protonated layered dititanate sheets is also discussed.

  14. A triangular prism solid and shell interactive mapping element for electromagnetic sheet metal forming process

    NASA Astrophysics Data System (ADS)

    Cui, Xiangyang; Li, She; Feng, Hui; Li, Guangyao

    2017-05-01

    In this paper, a novel triangular prism solid and shell interactive mapping element is proposed to solve the coupled magnetic-mechanical formulation in electromagnetic sheet metal forming process. A linear six-node "Triprism" element is firstly proposed for transient eddy current analysis in electromagnetic field. In present "Triprism" element, shape functions are given explicitly, and a cell-wise gradient smoothing operation is used to obtain the gradient matrices without evaluating derivatives of shape functions. In mechanical field analysis, a shear locking free triangular shell element is employed in internal force computation, and a data mapping method is developed to transfer the Lorentz force on solid into the external forces suffered by shell structure for dynamic elasto-plasticity deformation analysis. Based on the deformed triangular shell structure, a "Triprism" element generation rule is established for updated electromagnetic analysis, which means inter-transformation of meshes between the coupled fields can be performed automatically. In addition, the dynamic moving mesh is adopted for air mesh updating based on the deformation of sheet metal. A benchmark problem is carried out for confirming the accuracy of the proposed "Triprism" element in predicting flux density in electromagnetic field. Solutions of several EMF problems obtained by present work are compared with experiment results and those of traditional method, which are showing excellent performances of present interactive mapping element.

  15. Development of JSTAMP-Works/NV and HYSTAMP for Multipurpose Multistage Sheet Metal Forming Simulation

    NASA Astrophysics Data System (ADS)

    Umezu, Yasuyoshi; Watanabe, Yuko; Ma, Ninshu

    2005-08-01

    Since 1996, Japan Research Institute Limited (JRI) has been providing a sheet metal forming simulation system called JSTAMP-Works packaged the FEM solvers of LS-DYNA and JOH/NIKE, which might be the first multistage system at that time and has been enjoying good reputation among users in Japan. To match the recent needs, "faster, more accurate and easier", of process designers and CAE engineers, a new metal forming simulation system JSTAMP-Works/NV is developed. The JSTAMP-Works/NV packaged the automatic healing function of CAD and had much more new capabilities such as prediction of 3D trimming lines for flanging or hemming, remote control of solver execution for multi-stage forming processes and shape evaluation between FEM and CAD. On the other way, a multi-stage multi-purpose inverse FEM solver HYSTAMP is developed and will be soon put into market, which is approved to be very fast, quite accurate and robust. Lastly, authors will give some application examples of user defined ductile damage subroutine in LS-DYNA for the estimation of material failure and springback in metal forming simulation.

  16. 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.

  17. 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

  18. Frustration across the periodic table: heterolytic cleavage of dihydrogen by metal complexes.

    PubMed

    Bullock, R Morris; Chambers, Geoffrey M

    2017-08-28

    This perspective examines frustrated Lewis pairs (FLPs) in the context of heterolytic cleavage of H 2 by transition metal complexes, with an emphasis on molecular complexes bearing an intramolecular Lewis base. FLPs have traditionally been associated with main group compounds, yet many reactions of transition metal complexes support a broader classification of FLPs that includes certain types of transition metal complexes with reactivity resembling main group-based FLPs. This article surveys transition metal complexes that heterolytically cleave H 2 , which vary in the degree that the Lewis pairs within these systems interact. Many of the examples include complexes bearing a pendant amine functioning as the base with the metal functioning as the hydride acceptor. Consideration of transition metal compounds in the context of FLPs can inspire new innovations and improvements in transition metal catalysis.This article is part of the themed issue 'Frustrated Lewis pair chemistry'. © 2017 The Author(s).

  19. Analysis of acoustic emission during abrasive waterjet machining of sheet metals

    NASA Astrophysics Data System (ADS)

    Mokhtar, Nazrin; Gebremariam, MA; Zohari, H.; Azhari, Azmir

    2018-04-01

    The present paper reports on the analysis of acoustic emission (AE) produced during abrasive waterjet (AWJ) machining process. This paper focuses on the relationship of AE and surface quality of sheet metals. The changes in acoustic emission signals recorded by the mean of power spectral density (PSD) via covariance method in relation to the surface quality of the cut are discussed. The test was made using two materials for comparison namely aluminium 6061 and stainless steel 304 with five different feed rates. The acoustic emission data were captured by Labview and later processed using MATLAB software. The results show that the AE spectrums correlated with different feed rates and surface qualities. It can be concluded that the AE is capable of monitoring the changes of feed rate and surface quality.

  20. 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.

  1. Role of upwelling hydrothermal fluids in the development of alteration patterns at fast spreading ridges: Evidence from the sheeted dike complex at Pito Deep

    NASA Astrophysics Data System (ADS)

    Heft, Kerri L.; Gillis, Kathryn M.; Pollock, Megan A.; Karson, Jeffery A.; Klein, Emily M.

    2008-05-01

    Alteration of sheeted dikes exposed along submarine escarpments at the Pito Deep Rift (NE edge of the Easter microplate) provides constraints on the crustal component of axial hydrothermal systems at fast spreading mid-ocean ridges. Samples from vertical transects through the upper crust constrain the temporal and spatial scales of hydrothermal fluid flow and fluid-rock reaction. The dikes are relatively fresh (average extent of alteration is 27%), with the extent of alteration ranging from 0 to >80%. Alteration is heterogeneous on scales of tens to hundreds of meters and displays few systematic spatial trends. Background alteration is amphibole-dominated, with chlorite-rich dikes sporadically distributed throughout the dike complex, indicating that peak temperatures ranged from <300°C to >450°C and did not vary systematically with depth. Dikes locally show substantial metal mobility, with Zn and Cu depletion and Mn enrichment. Amphibole and chlorite fill fractures throughout the dike complex, whereas quartz-filled fractures and faults are only locally present. Regional variability in alteration characteristics is found on a scale of <1-2 km, illustrating the diversity of fluid-rock interaction that can be expected in fast spreading crust. We propose that much of the alteration in sheeted dike complexes develops within broad, hot upwelling zones, as the inferred conditions of alteration cannot be achieved in downwelling zones, particularly in the shallow dikes. Migration of circulating cells along rides axes and local evolution of fluid compositions produce sections of the upper crust with a distinctive character of alteration, on a scale of <1-2 km and <5-20 ka.

  2. Electrochemistry of mixed-metal bimetallic complexes containing the pentacyanoferrate(II) or pentaammineruthenium(II) metal center

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Moore, K.J.; Lee, L.; Mabbott, G.A.

    1983-03-30

    The electrochemistry of a series of mixed-metal bimetallic complexes of the type B/sub 5/MLM'B'/sub 5/, where B/sub 5/M = (CNN)/sub 5/Fe/sup II/ or (NH/sub 3/)/sub 5/Ru/sup II/, L = pyrazine, 4,4'-bipyridine, or 4-cyanopyridine, M'B'/sub 5/ = Rh/sup III/(NH/sub 3/)/sub 5/ or Co/sup III/(CN)/sub 5/, is reported. The bimetallic complexes all have metal-to-ligand charge-transfer (MLCT) bands associated with the M-B unit (d/sub ..pi../M ..-->.. p/sub ..pi../*L). The effect of the remote metal center, M'B'/sub 5/, is to function as a Lewis acid, shifting the MLCT maximum to lower energy and shifting the M/sup III///sup II/ reduction potential more positive with respectmore » to free B/sub 5/ML. The remote metal influence is attenuated by longer bridging ligands and by reduced ..pi..-overlap. A comparison of the electrochemical data of the mixed-valence Fe(II)/Fe(III) and Ru(II)/Ru(III) complexes to the mixed-metal Fe(II)/Co(III) and Ru(II)/Rh(III) complexes has enabled a quantitative measure of the stabilization due to electron delocalization in the mixed-valence complexes. The results show that electron delocalization is greater for the ruthenium complexes than for the iron complexes, is a small contributor to the total stabilization of the mixed-valence state, and even in ruthenium drops off rapidly as the length of the bridge increases.« less

  3. Identification of a process window for tailored carburization of sheet metals in hot stamping

    NASA Astrophysics Data System (ADS)

    Horn, Alexander; Merklein, Marion

    2018-05-01

    Due to governmental regulations concerning the reduction of CO2 emissions and increasing safety standards, hot stamping of high strength boron manganese steel sheets has evolved into a state of the art process for manufacturing structural car body parts. The combined forming and in-die quenching process enables the formation of a fully martensitic microstructure. Therefore, press hardened steels offer high strength, but low ductility. In order to further improve passenger safety, a tailored configuration of mechanical properties is desired. Besides state of the art methods, like the application of locally different heat treatment temperatures or varying quenching rates, the adjustment of mechanical properties of sheet metals by a tailored carburization is a novel approach. For the carburization process, the specimens are first coated with graphite and subsequently heat treated. Within this contribution, different coating strategies as well as heat treatment temperatures and dwell times are investigated. For the determination of a process window, mechanical properties such as tensile strength and microhardness will be analyzed and correlated with the resulting microstructure.

  4. Factors governing hole expansion ratio of steel sheets with smooth sheared edge

    NASA Astrophysics Data System (ADS)

    Yoon, Jae Ik; Jung, Jaimyun; Lee, Hak Hyeon; Kim, Gyo-Sung; Kim, Hyoung Seop

    2016-11-01

    Stretch-flangeability measured using hole expansion test (HET) represents the ability of a material to form into a complex shaped component. Despite its importance in automotive applications of advanced high strength steels, stretch-flangeability is a less known sheet metal forming property. In this paper, we investigate the factors governing hole expansion ratio (HER) by means of tensile test and HET. We correlate a wide range of tensile properties with HERs of steel sheet specimens because the stress state in the hole edge region during the HET is almost the same as that of the uniaxial tensile test. In order to evaluate an intrinsic HER of steel sheet specimens, the initial hole of the HET specimen is produced using a milling process after punching, which can remove accumulated shearing damage and micro-void in the hole edge region that is present when using the standard HER evaluation method. It was found that the intrinsic HER of steel sheet specimens was proportional to the strain rate sensitivity exponent and post uniform elongation.

  5. 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.

  6. 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.

  7. 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

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

    PubMed

    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.

  9. Complex-Morphology Metal-Based Nanostructures: Fabrication, Characterization, and Applications

    PubMed Central

    Gentile, Antonella; Ruffino, Francesco; Grimaldi, Maria Grazia

    2016-01-01

    Due to their peculiar qualities, metal-based nanostructures have been extensively used in applications such as catalysis, electronics, photography, and information storage, among others. New applications for metals in areas such as photonics, sensing, imaging, and medicine are also being developed. Significantly, most of these applications require the use of metals in the form of nanostructures with specific controlled properties. The properties of nanoscale metals are determined by a set of physical parameters that include size, shape, composition, and structure. In recent years, many research fields have focused on the synthesis of nanoscale-sized metallic materials with complex shape and composition in order to optimize the optical and electrical response of devices containing metallic nanostructures. The present paper aims to overview the most recent results—in terms of fabrication methodologies, characterization of the physico-chemical properties and applications—of complex-morphology metal-based nanostructures. The paper strongly focuses on the correlation between the complex morphology and the structures’ properties, showing how the morphological complexity (and its nanoscale control) can often give access to a wide range of innovative properties exploitable for innovative functional device production. We begin with an overview of the basic concepts on the correlation between structural and optical parameters of nanoscale metallic materials with complex shape and composition, and the possible solutions offered by nanotechnology in a large range of applications (catalysis, electronics, photonics, sensing). The aim is to assess the state of the art, and then show the innovative contributions that can be proposed in this research field. We subsequently report on innovative, versatile and low-cost synthesis techniques, suitable for providing a good control on the size, surface density, composition and geometry of the metallic nanostructures. The main

  10. Metal-Metal Interactions in Heterobimetallic Complexes with Dinucleating Redox-Active Ligands.

    PubMed

    Broere, Daniël L J; Modder, Dieuwertje K; Blokker, Eva; Siegler, Maxime A; van der Vlugt, Jarl Ivar

    2016-02-12

    The tuning of metal-metal interactions in multinuclear assemblies is a challenge. Selective P coordination of a redox-active PNO ligand to Au(I) followed by homoleptic metalation of the NO pocket with Ni(II) affords a unique trinuclear Au-Ni-Au complex. This species features two antiferromagnetically coupled ligand-centered radicals and a double intramolecular d(8)-d(10) interaction, as supported by spectroscopic, single-crystal X-ray diffraction, and computational data. A corresponding cationic dinuclear Au-Ni analogue with a stronger d(8)-d(10) interaction is also reported. Although both heterobimetallic structures display rich electrochemistry, only the trinuclear Au-Ni-Au complex facilitates electrocatalytic C-X bond activation of alkyl halides in its doubly reduced state. Hence, the presence of a redox-active ligand framework, an available coordination site at gold, and the nature of the nickel-gold interaction appear to be essential for this reactivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. 40 CFR 721.4680 - Metal salts of complex inorganic oxyacids (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Metal salts of complex inorganic... New Uses for Specific Chemical Substances § 721.4680 Metal salts of complex inorganic oxyacids... substances identified generically as metal salts of complex inorganic oxyacids (PMNs P-89-576 and P-89-577...

  12. 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.

  13. Fabrication of carbon nanotube films from alkyne-transition metal complexes

    DOEpatents

    Iyer, Vivekanantan S [Delft, NL; Vollhardt, K Peter C. [Oakland, CA

    2007-08-28

    A simple method for the production or synthesis of carbon nanotubes as free-standing films or nanotube mats by the thermal decomposition of transition metal complexed alkynes with aryl, alkyl, alkenyl, or alkynyl substituents. In particular, transition metal (e.g. Co, Ni, Fe, Mo) complexes of diarylacetylenes, e.g. diphenylacetylene, and solid mixtures of these complexes with suitable, additional carbon sources are heated in a vessel. More specifically, the heating of the transition metal complex is completed at a temperature between 400-800.degree. C. and more particularly 550-700.degree. C. for between 0.1 to 24 hours and more particularly 0.5-3 hours in a sealed vessel under a partial pressure of argon or helium.

  14. New developments in tribomechanical modeling of automotive sheet steel forming

    NASA Astrophysics Data System (ADS)

    Khandeparkar, Tushar; Chezan, Toni; van Beeck, Jeroen

    2018-05-01

    Forming of automotive sheet metal body panels is a complex process influenced by both the material properties and contact conditions in the forming tooling. Material properties are described by the material constitutive behavior and the material flow into the forming die can be described by the tribological system. This paper investigates the prediction accuracy of the forming process using the Tata Steel state of the art description of the material constitutive behavior in combination with different friction models. A cross-die experiment is used to investigate the accuracy of local deformation modes typically seen in automotive sheet metal forming operations. Results of advanced friction models as well as the classical Coulomb friction description are compared to the experimentally measured strain distribution and material draw-in. Two hot-dip galvanized coated steel forming grades were used for the investigations. The results show that the accuracy of the simulation is not guaranteed by the advanced friction models for the entire investigated blank holder force range, both globally and locally. A measurable difference between the calculated and measured local strains is seen for both studied models even in the case where the global indicator, i.e. the draw-in, is well predicted.

  15. Nonlinear d10-ML2 Transition-Metal Complexes

    PubMed Central

    Wolters, Lando P; Bickelhaupt, F Matthias

    2013-01-01

    We have investigated the molecular geometries of a series of dicoordinated d10-transition-metal complexes ML2 (M=Co−, Rh−, Ir−, Ni, Pd, Pt, Cu+, Ag+, Au+; L=NH3, PH3, CO) using relativistic density functional theory (DFT) at ZORA-BLYP/TZ2P. Not all complexes have the expected linear ligand–metal–ligand (L–M–L) angle: this angle varies from 180° to 128.6° as a function of the metal as well as the ligands. Our main objective is to present a detailed explanation why ML2 complexes can become bent. To this end, we have analyzed the bonding mechanism in ML2 as a function of the L–M–L angle using quantitative Kohn–Sham molecular orbital (MO) theory in combination with an energy decomposition analysis (EDA) scheme. The origin of bent L–M–L structures is π backdonation. In situations of strong π backdonation, smaller angles increase the overlap of the ligand’s acceptor orbital with a higher-energy donor orbital on the metal-ligand fragment, and therefore favor π backdonation, resulting in additional stabilization. The angle of the complexes thus depends on the balance between this additional stabilization and increased steric repulsion that occurs as the complexes are bent. PMID:24551547

  16. Frustration across the periodic table: heterolytic cleavage of dihydrogen by metal complexes

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Bullock, R. Morris; Chambers, Geoffrey M.

    2017-07-24

    This Perspective examines the field of Frustrated Lewis Pairs (FLPs) in the context of transition metal mediated heterolytic cleavage of H2, with a particular emphasis on molecular complexes bearing an intramolecular Lewis base. FLPs have traditionally been associated with group compounds, yet many transition metal reactions support a broader classification of FLPs to include certain types of transition metal complexes with reactivity resembling main group based FLPs. This article surveys transition metal complexes that heterolytically cleave H2, which vary in the degree that the Lewis pairs within these systems interact. Particular attention is focused on complexes bearing a pendant aminemore » function as the base. Consideration of transition metal compounds in the context of FLPs can inspire new innovations and improvements in transition metal catalysis.« less

  17. 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.

  18. Trace Metal-Humic Complexes in Natural Waters: Insights From Speciation Experiments

    NASA Astrophysics Data System (ADS)

    Stern, J. C.; Salters, V.; Sonke, J.

    2006-12-01

    The DOM cycle is intimately linked to the cycling and bioavailability of trace metals in aqueous environments. The presence or absence of DOM in the water column can determined whether trace elements will be present in limited quantities as a nutrient, or in surplus quantities as a toxicant. Humic substances (HS), which represent the refractory products of DOM degradation, strongly affect the speciation of trace metals in natural waters. To simulate metal-HS interactions in nature, experiments must be carried out using trace metal concentrations. Sensitive detection systems such as ICP-MS make working with small (nanomolar) concentrations possible. Capillary electrophoresis coupled with ICP-MS (CE-ICP-MS) has recently been identified as a rapid and accurate method to separate metal species and calculate conditional binding constants (log K_c) of metal-humic complexes. CE-ICP-MS was used to measure partitioning of metals between humic substances and a competing ligand (EDTA) and calculate binding constants of rare earth element (REE) and Th, Hf, and Zr-humic complexes at pH 3.5-8 and ionic strength of 0.1. Equilibrium dialysis ligand exchange (EDLE) experiments to validate the CE-ICP-MS method were performed to separate the metal-HS and metal-EDTA species by partitioning due to size exclusion via diffusion through a 1000 Da membrane. CE-ICP-MS experiments were also conducted to compare binding constants of REE with humic substances of various origin, including soil, peat, and aquatic DOM. Results of our experiments show an increase in log K_c with decrease in ionic radius for REE-humic complexes (the lanthanide contraction effect). Conditional binding constants of tetravalent metal-humic complexes were found to be several orders of magnitude higher than REE-humic complexes, indicating that tetravalent metals have a very strong affinity for humic substances. Because thorium is often used as a proxy for the tetravalent actinides, Th-HS binding constants can allow us

  19. Synthesis and structural characterisation of alkali metal complexes of heteroatom-stabilised 1,4- and 1,6-dicarbanions.

    PubMed

    Izod, Keith; Bowman, Lyndsey J; Wills, Corinne; Clegg, William; Harrington, Ross W

    2009-05-07

    A straightforward Peterson olefination reaction between either [{(Me(2)PhSi)(3)C}Li(THF)] or in situ-generated [(Me(3)Si)(2){Ph(2)P(BH(3))}CLi(THF)(n)] and paraformaldehyde gives the alkenes (Me(2)PhSi)(2)C[double bond, length as m-dash]CH(2) () and (Me(3)Si){Ph(2)P(BH(3))}C[double bond, length as m-dash]CH(2) (), respectively, in good yield. Ultrasonic treatment of with lithium in THF yields the lithium complex [{(Me(2)PhSi)(2)C(CH(2))}Li(THF)(n)](2) (), which reacts in situ with one equivalent of KOBu(t) in diethyl ether to give the potassium salt [{(Me(2)PhSi)(2)C(CH(2))}K(THF)](2) (). Similarly, ultrasonic treatment of with lithium in THF yields the lithium complex [[{Ph(2)P(BH(3))}(Me(3)Si)C(CH(2))]Li(THF)(3)](2).2THF (). The bis(phosphine-borane) [(Me(3)Si){Me(2)(H(3)B)P}CH(Me(2)Si)(CH(2))](2) () may be prepared by the reaction of [Me(2)P(BH(3))CH(SiMe(3))]Li with half an equivalent of ClSiMe(2)CH(2)CH(2)SiMe(2)Cl in refluxing THF. Metalation of with two equivalents of MeLi in refluxing THF yields the lithium complex [[{Me(2)P(BH(3))}(Me(3)Si)C{(SiMe(2))(CH(2))}]Li(THF)(3)](2) (), whereas metalation with two equivalents of MeK in cold diethyl ether yields the potassium complex [[{Me(2)P(BH(3))}(Me(3)Si)C{(SiMe(2))(CH(2))}](2)K(2)(THF)(4)](infinity) () after recrystallisation. X-Ray crystallography shows that, whereas the lithium complex crystallises as a discrete molecular species, the potassium complexes and crystallise as sheet and chain polymers, respectively.

  20. 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.

  1. The build-up, configuration, and dynamical sensitivity of the Eurasian ice-sheet complex to Late Weichselian climatic and oceanic forcing

    NASA Astrophysics Data System (ADS)

    Patton, Henry; Hubbard, Alun; Andreassen, Karin; Winsborrow, Monica; Stroeven, Arjen P.

    2016-12-01

    The Eurasian ice-sheet complex (EISC) was the third largest ice mass during the Last Glacial Maximum (LGM), after the Antarctic and North American ice sheets. Despite its global significance, a comprehensive account of its evolution from independent nucleation centres to its maximum extent is conspicuously lacking. Here, a first-order, thermomechanical model, robustly constrained by empirical evidence, is used to investigate the dynamics of the EISC throughout its build-up to its maximum configuration. The ice flow model is coupled to a reference climate and applied at 10 km spatial resolution across a domain that includes the three main spreading centres of the Celtic, Fennoscandian and Barents Sea ice sheets. The model is forced with the NGRIP palaeo-isotope curve from 37 ka BP onwards and model skill is assessed against collated flowsets, marginal moraines, exposure ages and relative sea-level history. The evolution of the EISC to its LGM configuration was complex and asynchronous; the western, maritime margins of the Fennoscandian and Celtic ice sheets responded rapidly and advanced across their continental shelves by 29 ka BP, yet the maximum aerial extent (5.48 × 106 km2) and volume (7.18 × 106 km3) of the ice complex was attained some 6 ka later at c. 22.7 ka BP. This maximum stand was short-lived as the North Sea and Atlantic margins were already in retreat whilst eastern margins were still advancing up until c. 20 ka BP. High rates of basal erosion are modelled beneath ice streams and outlet glaciers draining the Celtic and Fennoscandian ice sheets with extensive preservation elsewhere due to frozen subglacial conditions, including much of the Barents and Kara seas. Here, and elsewhere across the Norwegian shelf and North Sea, high pressure subglacial conditions would have promoted localised gas hydrate formation.

  2. 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.

  3. 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…

  4. Selenophene transition metal complexes

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    White, Carter James

    1994-07-27

    This research shows that selenophene transition metal complexes have a chemistry that is similar to their thiophene analogs. Selenophene coordination has been demonstrated and confirmed by molecular structure in both the η 5- and the η 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 77Se NMR chemical shift values for selenophene complexes fall within distinct regions primarily depending on the coordination mode of the selenophene ligand.more » In the final paper, the C-H bond activation of η 1(S)-bound thiophenes, η 1(S)-benzothiophene and η 1(Se)-bound selenophenes has been demonstrated. The deprotonation and rearrangement of the η 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 3)Re(2-benzothioenylcarbene)]O 3SCF 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 η 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.« less

  5. Robot-based additive manufacturing for flexible die-modelling in incremental sheet forming

    NASA Astrophysics Data System (ADS)

    Rieger, Michael; Störkle, Denis Daniel; Thyssen, Lars; Kuhlenkötter, Bernd

    2017-10-01

    The paper describes the application concept of additive manufactured dies to support the robot-based incremental sheet metal forming process (`Roboforming') for the production of sheet metal components in small batch sizes. Compared to the dieless kinematic-based generation of a shape by means of two cooperating industrial robots, the supporting robot models a die on the back of the metal sheet by using the robot-based fused layer manufacturing process (FLM). This tool chain is software-defined and preserves the high geometrical form flexibility of Roboforming while flexibly generating support structures adapted to the final part's geometry. Test series serve to confirm the feasibility of the concept by investigating the process challenges of the adhesion to the sheet surface and the general stability as well as the influence on the geometric accuracy compared to the well-known forming strategies.

  6. Application Of A New Semi-Empirical Model For Forming Limit Prediction Of Sheet Material Including Superposed Loads Of Bending And Shearing

    NASA Astrophysics Data System (ADS)

    Held, Christian; Liewald, Mathias; Schleich, Ralf; Sindel, Manfred

    2010-06-01

    The use of lightweight materials offers substantial strength and weight advantages in car body design. Unfortunately such kinds of sheet material are more susceptible to wrinkling, spring back and fracture during press shop operations. For characterization of capability of sheet material dedicated to deep drawing processes in the automotive industry, mainly Forming Limit Diagrams (FLD) are used. However, new investigations at the Institute for Metal Forming Technology have shown that High Strength Steel Sheet Material and Aluminum Alloys show increased formability in case of bending loads are superposed to stretching loads. Likewise, by superposing shearing on in plane uniaxial or biaxial tension formability changes because of materials crystallographic texture. Such mixed stress and strain conditions including bending and shearing effects can occur in deep-drawing processes of complex car body parts as well as subsequent forming operations like flanging. But changes in formability cannot be described by using the conventional FLC. Hence, for purpose of improvement of failure prediction in numerical simulation codes significant failure criteria for these strain conditions are missing. Considering such aspects in defining suitable failure criteria which is easy to implement into FEA a new semi-empirical model has been developed considering the effect of bending and shearing in sheet metals formability. This failure criterion consists of the combination of the so called cFLC (combined Forming Limit Curve), which considers superposed bending load conditions and the SFLC (Shear Forming Limit Curve), which again includes the effect of shearing on sheet metal's formability.

  7. Complexation-induced supramolecular assembly drives metal-ion extraction.

    PubMed

    Ellis, Ross J; Meridiano, Yannick; Muller, Julie; Berthon, Laurence; Guilbaud, Philippe; Zorz, Nicole; Antonio, Mark R; Demars, Thomas; Zemb, Thomas

    2014-09-26

    Combining experiment with theory reveals the role of self-assembly and complexation in metal-ion transfer through the water-oil interface. The coordinating metal salt Eu(NO3)3 was extracted from water into oil by a lipophilic neutral amphiphile. Molecular dynamics simulations were coupled to experimental spectroscopic and X-ray scattering techniques to investigate how local coordination interactions between the metal ion and ligands in the organic phase combine with long-range interactions to produce spontaneous changes in the solvent microstructure. Extraction of the Eu(3+)-3(NO3(-)) ion pairs involves incorporation of the "hard" metal complex into the core of "soft" aggregates. This seeds the formation of reverse micelles that draw the water and "free" amphiphile into nanoscale hydrophilic domains. The reverse micelles interact through attractive van der Waals interactions and coalesce into rod-shaped polynuclear Eu(III) -containing aggregates with metal centers bridged by nitrate. These preorganized hydrophilic domains, containing high densities of O-donor ligands and anions, provide improved Eu(III) solvation environments that help drive interfacial transfer, as is reflected by the increasing Eu(III) partitioning ratios (oil/aqueous) despite the organic phase approaching saturation. For the first time, this multiscale approach links metal-ion coordination with nanoscale structure to reveal the free-energy balance that drives the phase transfer of neutral metal salts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Ultrafast photophysics of transition metal complexes.

    PubMed

    Chergui, Majed

    2015-03-17

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

  9. Water-in-Supercritical CO2 Microemulsion Stabilized by a Metal Complex.

    PubMed

    Luo, Tian; Zhang, Jianling; Tan, Xiuniang; Liu, Chengcheng; Wu, Tianbin; Li, Wei; Sang, Xinxin; Han, Buxing; Li, Zhihong; Mo, Guang; Xing, Xueqing; Wu, Zhonghua

    2016-10-17

    Herein we propose for the first time the utilization of a metal complex for forming water-in-supercritical CO 2 (scCO 2 ) microemulsions. The water solubility in the metal-complex-stabilized microemulsion is significantly improved compared with the conventional water-in-scCO 2 microemulsions stabilized by hydrocarbons. Such a microemulsion provides a promising route for the in situ CO 2 reduction catalyzed by a metal complex at the water/scCO 2 interface. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. 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.

  11. Local laser-strengthening: Customizing the forming behavior of car body steel sheets

    NASA Astrophysics Data System (ADS)

    Wagner, M.; Jahn, A.; Beyer, E.; Balzani, D.

    2018-05-01

    Future trends in designing lightweight components especially for automotive applications increasingly require complex and delicate structures with highest possible level of capacity [1]. The manufacturing of metallic car body components is primarily realized by deep or stretch drawing. The forming process of especially cold rolled and large-sized components is typically characterized by inhomogeneous stress and strain distributions. As a result, the avoidance of undesirable deep drawing effects like earing and local necking is among the greatest challenges in forming complex car body structures [2]. Hence, a novel local laser-treatment approach with the objective of customizing the forming behavior of car body steel sheets is currently explored.

  12. Structural analysis of the coordination of dinitrogen to transition metal complexes.

    PubMed

    Peigné, Benjamin; Aullón, Gabriel

    2015-06-01

    Transition-metal complexes show a wide variety of coordination modes for the nitrogen molecule. A structural database study has been undertaken for dinitrogen complexes, and geometrical parameters around the L(n)M-N2 unit are retrieved from the Cambridge Structural Database. These data were classified in families of compounds, according to metal properties, to determine the degree of lengthening for the dinitrogen bonding. The importance of the nature of the metal center, such as coordination number and electronic configuration, is reported. Our study reveals poor activation by coordination of dinitrogen in mononuclear complexes, always having end-on coordination. However, partial weakening of nitrogen-nitrogen bonding is found for end-on binuclear complexes, whereas side-on complexes can be completely activated.

  13. kW-class direct diode laser for sheet metal cutting based on commercial pump modules

    NASA Astrophysics Data System (ADS)

    Witte, U.; Schneider, F.; Holly, C.; Di Meo, A.; Rubel, D.; Boergmann, F.; Traub, M.; Hoffmann, D.; Drovs, S.; Brand, T.; Unger, A.

    2017-02-01

    We present a direct diode laser with an optical output power of more than 800 W ex 100 μm with an NA of 0.17. The system is based on 6 commercial pump modules that are wavelength stabilized by use of VBGs. Dielectric filters are used for coarse and dense wavelength multiplexing. Metal sheet cutting tests were performed in order to prove system performance and reliability. Based on a detailed analysis of loss mechanisms, we show that the design can be easily scaled to output powers in the range of 2 kW and to an optical efficiency of 80%.

  14. 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%.

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

    DOE PAGES

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

    2015-08-11

    A series of alkali metal cerium diphenylhydrazido complexes, M x(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. Reductionmore » 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.« less

  16. Synthesis and Spectral Characterization of Antifungal Sensitive Schiff Base Transition Metal Complexes

    PubMed Central

    Sakthivel, A.; Rajasekaran, K.

    2007-01-01

    New N2O2 donor type Schiff base has been designed and synthesized by condensing acetoacetanilido-4-aminoantipyrine with 2-aminobenzoic acid in ethanol. Solid metal complexes of the Schiff base with Cu(II), Ni(II), Co(II), Mn(II), Zn(II), VO(IV), Hg(II) and Cd(II) metal ions were synthesized and characterized by elemental analyses, magnetic susceptibility, molar conduction, fast atom bombardment (FAB) mass, IR, UV-Vis, and 1H NMR spectral studies. The data show that the complexes have the composition of ML type. The UV-Vis. and magnetic susceptibility data of the complexes suggest a square-planar geometry around the central metal ion except VO(IV) complex which has square-pyramidal geometry. The in vitro antifungal activities of the compounds were tested against fungi such as Aspergillus niger, Aspergillus flavus, Rhizopus stolonifer, Candida albicans, Rhizoctonia bataicola and Trichoderma harizanum. All the metal complexes showed stronger antifungal activities than the free ligand. The minimum inhibitory concentrations (MIC) of the metal complexes were found in the range of 10~31 µg/ml. PMID:24015086

  17. Anticancer activity of metal complexes: involvement of redox processes.

    PubMed

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

    2011-08-15

    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.

  18. 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

  19. 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)

  20. Anharmonic Vibrational Spectroscopy on Metal Transition Complexes

    NASA Astrophysics Data System (ADS)

    Latouche, Camille; Bloino, Julien; Barone, Vincenzo

    2014-06-01

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

  1. Superabsorbing, Artificial Metal Films Constructed from Semiconductor Nanoantennas.

    PubMed

    Kim, Soo Jin; Park, Junghyun; Esfandyarpour, Majid; Pecora, Emanuele F; Kik, Pieter G; Brongersma, Mark L

    2016-06-08

    In 1934, Wilhelm Woltersdorff demonstrated that the absorption of light in an ultrathin, freestanding film is fundamentally limited to 50%. He concluded that reaching this limit would require a film with a real-valued sheet resistance that is exactly equal to R = η/2 ≈ 188.5Ω/□, where [Formula: see text] is the impedance of free space. This condition can be closely approximated over a wide frequency range in metals that feature a large imaginary relative permittivity εr″, that is, a real-valued conductivity σ = ε0εr″ω. A thin, continuous sheet of semiconductor material does not facilitate such strong absorption as its complex-valued permittivity with both large real and imaginary components preclude effective impedance matching. In this work, we show how a semiconductor metafilm constructed from optically resonant semiconductor nanostructures can be created whose optical response mimics that of a metallic sheet. For this reason, the fundamental absorption limit mentioned above can also be reached with semiconductor materials, opening up new opportunities for the design of ultrathin optoelectronic and light harvesting devices.

  2. [Ultraviolet-visible spectrometry analysis of insoluble xanthate heavy metal complexes].

    PubMed

    Qiu, Bo; Liu, Jin-Feng; Liu, Yao-Chi; Yang, Zhao-Guang; Li, Hai-Pu

    2014-11-01

    A ultraviolet-visible spectrometry method of determining insoluble xanthate heavy metal complexes in flotation wastewater was the first time to be put forward. In this work, the changes of ultraviolet-visible spectra of xanthate solution after the addition of various heavy metal ions were investigated firstly. It was found that Pb2+ and Cu2+ can form insoluble complexes with xanthate, while Fe2+, Zn2+ and Mn2+ have little effect on the ultraviolet absorption of xanthate solution. Then the removal efficiencies of filter membrane with different pore sizes were compared, and the 0.22 μm membrane was found to be effective to separate copper xanthate or lead xanthate from the filtrate. Furthermore, the results of the study on the reaction of sodium sulfide and insoluble xanthate heavy metal complexes showed that S(2-) can release the xanthate ion quantitatively from insoluble complexes to solution. Based on the above research, it was concluded that the amount of insoluble xanthate heavy metal complexes in water samples can be obtained through the increase of free xanthate in the filtrate after the addition of sodium sulfide. Finally, the feasibility of this method was verified by the application to the analysis of flotation wastewater from three ore-dressing plants in the Thirty-six Coves in Chenzhou.

  3. Self-assembly of discrete metal complexes in aqueous solution via block copolypeptide amphiphiles.

    PubMed

    Kuroiwa, Keita; Masaki, Yoshitaka; Koga, Yuko; Deming, Timothy J

    2013-01-21

    The integration of discrete metal complexes has been attracting significant interest due to the potential of these materials for soft metal-metal interactions and supramolecular assembly. Additionally, block copolypeptide amphiphiles have been investigated concerning their capacity for self-assembly into structures such as nanoparticles, nanosheets and nanofibers. In this study, we combined these two concepts by investigating the self-assembly of discrete metal complexes in aqueous solution using block copolypeptides. Normally, discrete metal complexes such as [Au(CN)(2)]-, when molecularly dispersed in water, cannot interact with one another. Our results demonstrated, however, that the addition of block copolypeptide amphiphiles such as K(183)L(19) to [Au(CN)(2)]- solutions induced one-dimensional integration of the discrete metal complex, resulting in photoluminescence originating from multinuclear complexes with metal-metal interactions. Transmission electron microscopy (TEM) showed a fibrous nanostructure with lengths and widths of approximately 100 and 20 nm, respectively, which grew to form advanced nanoarchitectures, including those resembling the weave patterns of Waraji (traditional Japanese straw sandals). This concept of combining block copolypeptide amphiphiles with discrete coordination compounds allows the design of flexible and functional supramolecular coordination systems in water.

  4. Single point incremental forming: Formability of PC sheets

    NASA Astrophysics Data System (ADS)

    Formisano, A.; Boccarusso, L.; Carrino, L.; Lambiase, F.; Minutolo, F. Memola Capece

    2018-05-01

    Recent research on Single Point Incremental Forming of polymers has slightly covered the possibility of expanding the materials capability window of this flexible forming process beyond metals, by demonstrating the workability of thermoplastic polymers at room temperature. Given the different behaviour of polymers compared to metals, different aspects need to be deepened to better understand the behaviour of these materials when incrementally formed. Thus, the aim of the work is to investigate the formability of incrementally formed polycarbonate thin sheets. To this end, an experimental investigation at room temperature was conducted involving formability tests; varying wall angle cone and pyramid frusta were manufactured by processing polycarbonate sheets with different thicknesses and using tools with different diameters, in order to draw conclusions on the formability of polymer sheets through the evaluation of the forming angles and the observation of the failure mechanisms.

  5. Drug Delivery Systems For Anti-Cancer Active Complexes of Some Coinage Metals.

    PubMed

    Zhang, Ming; Saint-Germain, Camille; He, Guiling; Sun, Raymond Wai-Yin

    2018-02-12

    Although cisplatin and a number of platinum complexes have widely been used for the treatment of neoplasia, patients receiving these treatments have frequently suffered from their severe toxic side effects, the development of resistance with consequent relapse. In the recent decades, numerous complexes of coinage metals including that of gold, copper and silver have been reported to display promising in vitro and/or in vivo anti-cancer activities as well as potent activities towards cisplatin-resistant tumors. Nevertheless, the medical development of these metal complexes has been hampered by their instability in aqueous solutions and the nonspecific binding in biological systems. One of the approaches to overcome these problems is to design and develop adequate drug delivery systems (DDSs) for the transport of these complexes. By functionalization, encapsulation or formulation of the metal complexes, several types of DDSs have been reported to improve the desired pharmacological profile of the metal complexes, improving their overall stability, bioavailability, anti-cancer activity and reducing their toxicity towards normal cells. In this review, we summarized the recent findings for different DDSs for various anti- cancer active complexes of some coinage metals. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  6. 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.

  7. Communication Fact Sheets for Parents.

    ERIC Educational Resources Information Center

    Stremel, Kathleen; Bixler, Betsy; Morgan, Susanne; Layton, Kristen

    This booklet contains 28 fact sheets on communication written primarily for parents and families with a child who is deaf-blind. They attempt to address fundamental but complex issues related to the communication needs of children with vision and hearing impairments. Each fact sheet targets a specific area, including: (1) communication; (2)…

  8. Method of manufacturing aluminide sheet by thermomechanical processing of aluminide powders

    DOEpatents

    Hajaligol, Mohammad R.; Scorey, Clive; Sikka, Vinod K.; Deevi, Seetharama C.; Fleishhauer, Grier; Lilly, Jr., A. Clifton; German, Randall M.

    2003-12-09

    A powder metallurgical process of preparing a sheet from a powder having an intermetallic alloy composition such as an iron, nickel or titanium aluminide. The sheet can be manufactured into electrical resistance heating elements having improved room temperature ductility, electrical resistivity, cyclic fatigue resistance, high temperature oxidation resistance, low and high temperature strength, and/or resistance to high temperature sagging. The iron aluminide has an entirely ferritic microstructure which is free of austenite and can include, in weight %, 4 to 32% Al, and optional additions such as .ltoreq.1% Cr, .gtoreq.0.05% Zr .ltoreq.2% Ti, .ltoreq.2% Mo, .ltoreq.1% Ni, .ltoreq.0.75% C, .ltoreq.0.1% B, .ltoreq.1% submicron oxide particles and/or electrically insulating or electrically conductive covalent ceramic particles, .ltoreq.1% rare earth metal, and/or .ltoreq.3% Cu. The process includes forming a non-densified metal sheet by consolidating a powder having an intermetallic alloy composition such as by roll compaction, tape casting or plasma spraying, forming a cold rolled sheet by cold rolling the non-densified metal sheet so as to increase the density and reduce the thickness thereof and annealing the cold rolled sheet. The powder can be a water, polymer or gas atomized powder which is subjecting to sieving and/or blending with a binder prior to the consolidation step. After the consolidation step, the sheet can be partially sintered. The cold rolling and/or annealing steps can be repeated to achieve the desired sheet thickness and properties. The annealing can be carried out in a vacuum furnace with a vacuum or inert atmosphere. During final annealing, the cold rolled sheet recrystallizes to an average grain size of about 10 to 30 .mu.m. Final stress relief annealing can be carried out in the B2 phase temperature range.

  9. Method of manufacturing aluminide sheet by thermomechanical processing of aluminide powders

    DOEpatents

    Hajaligol, Mohammad R.; Scorey, Clive; Sikka, Vinod K.; Deevi, Seetharama C.; Fleischhauer, Grier; Lilly, Jr., A. Clifton; German, Randall M.

    2000-01-01

    A powder metallurgical process of preparing a sheet from a powder having an intermetallic alloy composition such as an iron, nickel or titanium aluminide. The sheet can be manufactured into electrical resistance heating elements having improved room temperature ductility, electrical resistivity, cyclic fatigue resistance, high temperature oxidation resistance, low and high temperature strength, and/or resistance to high temperature sagging. The iron aluminide has an entirely ferritic microstructure which is free of austenite and can include, in weight %, 4 to 32% Al, and optional additions such as .ltoreq.1% Cr, .gtoreq.0.05% Zr.ltoreq.2% Ti, .ltoreq.2% Mo, .ltoreq.1% Ni, .ltoreq.0.75% C, .ltoreq.0.1% B, .ltoreq.1% submicron oxide particles and/or electrically insulating or electrically conductive covalent ceramic particles, .ltoreq.1% rare earth metal, and/or .ltoreq.3% Cu. The process includes forming a non-densified metal sheet by consolidating a powder having an intermetallic alloy composition such as by roll compaction, tape casting or plasma spraying, forming a cold rolled sheet by cold rolling the non-densified metal sheet so as to increase the density and reduce the thickness thereof and annealing the cold rolled sheet. The powder can be a water, polymer or gas atomized powder which is subjecting to sieving and/or blending with a binder prior to the consolidation step. After the consolidation step, the sheet can be partially sintered. The cold rolling and/or annealing steps can be repeated to achieve the desired sheet thickness and properties. The annealing can be carried out in a vacuum furnace with a vacuum or inert atmosphere. During final annealing, the cold rolled sheet recrystallizes to an average grain size of about 10 to 30 .mu.m. Final stress relief annealing can be carried out in the B2 phase temperature range.

  10. Features of proteolytic properties of tetraphenylporphyrin complex with lanthanide group metals

    NASA Astrophysics Data System (ADS)

    Tobolkina, Elena A.; Skripnikova, Tatiana A.; Starikova, Anna A.; Shumilova, Galina I.; Pendin, Andrey A.

    2018-01-01

    Demetallation of metalloporphyrin molecules is one of the essential degradation reactions in photosynthesis. The effect of metalloporphyrin nature on removal of central metals from tetraphenylporphyrin complexes based on lanthanide group metals (Dy, Er, Lu, Ho) has been studied. pH values, at which the metal ions leave the metalloporphyrin complex were established using two-phase spectrophotometric titration with potentiometric pH-control. The pH values decrease with the increase of atomic numbers of lanthanide groups, as well as with increase of 4f-electrons. The reaction of an extra ligand exchange for the hydroxide ion was studied. For Dy-, Er- and Ho-tetraphenylporphyrin complexes one particle of extra ligand coordinates with one porphyrin complex. A complex with dimeric particles can be formed for the system of Lu-tetraphenylporphyrin. Constants of the ion exchange reactions were calculated.

  11. Flexible Ceramic-Metal Insulation Composite and Method of Making

    NASA Technical Reports Server (NTRS)

    Rasky, Daniel J. (Inventor); Sawko, Paul M. (Inventor); Kilodziej, Paul (Inventor); Kourtides, Demetrius A. (Inventor)

    1998-01-01

    A method for joining a woven flexible ceramic fabric and a thin metal sheet creating an integral metal surfaced flexible thermal protection article, which methods compress: placing multiple dots of high temperature metallic or fabric and the thin metal sheet in a random or organized pattern, with the proviso that the brazing material covers about 10% or less of the surface of one flat side of the metal sheet; heating the flexible ceramic fabric, brazing material and thin metal sheet for a predetermined period of time to integrally connect the same; and cooling the formed flexible article to ambient temperature. Preferably the flexible ceramic is selected from fibers comprising atoms of silicon, carbon, nitrogen, boron, oxygen or combinations thereof. The flexible thermal protection article produced is also part of the present invention. The thin metal sheet is comprised of titanium, aluminum, chromium, niobium or alloys or combinations thereof. The brazing material is selected from copper/silver or copper/gold or is a ceramic brazing or adhesive material.

  12. Interactions of platinum metals and their complexes in biological systems.

    PubMed Central

    LeRoy, A F

    1975-01-01

    Platinum-metal oxidation catalysts are to be introduced in exhaust systems of many 1975 model-year automobiles in the U.S. to meet Clean Air Act standards. Small quantities of finely divided catalyst have been found issuing from prototype systems; platinum and palladium compounds may be found also. Although platinum exhibits a remarkable resistance to oxidation and chemical attack, it reacts chemically under some conditions producing coordination complex compounds. Palladium reacts more readily than platinum. Some platinum-metal complexes interact with biological systems as bacteriostatic, bacteriocidal, viricidal, and immunosuppressive agents. Workers chronically exposed to platinum complexes often develop asthma-like respiratory distress and skin reactions called platinosis. Platinum complexes used alone and in combination therapy with other drugs have recently emerged as effective agents in cancer chemotherapy. Understanding toxic and favorable interactions of metal species with living organisms requires basic information on quantities and chemical characteristics of complexes at trace concentrations in biological materials. Some basic chemical kinetic and thermodynamic data are presented to characterize the chemical behavior of the complex cis-[Pt(NH3)2Cl2] used therapeutically. A brief discussion of platinum at manogram levels in biological tissue is discussed. PMID:50943

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. Study of distorted octahedral structure in 3d transition metal complexes using XAFS

    NASA Astrophysics Data System (ADS)

    Gaur, A.; Nitin Nair, N.; Shrivastava, B. D.; Das, B. K.; Chakrabortty, Monideepa; Jha, S. N.; Bhattacharyya, D.

    2018-01-01

    Distortion in octahedral structure of 3d transition metal complexes (Mn, Fe, Co, Ni, Cu, Zn) has been studied using XAFS showing divergent nature of Cu complex. EXAFS analysis showed elongated metal-oxygen bonds for Cu complex leading to more distorted structure. Derivative XANES spectrum at Cu K-edge exhibits splitting of main edge which is correlated to elongated Cu-O bond length. Using these coordination geometry around metal centers, theoretical XANES spectra have been generated and features observed have been correlated to the corresponding metals p-DOS. It has been shown that distorted octahedral field in Cu complex is responsible for splitting of p-DOS.

  18. Synthesis, spectral studies and biological evaluation of 2-aminonicotinic acid metal complexes.

    PubMed

    Nawaz, Muhammad; Abbasi, Muhammad Waseem; Hisaindee, Soleiman; Zaki, Muhammad Javed; Abbas, Hira Fatima; Mengting, Hu; Ahmed, M Arif

    2016-05-15

    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. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Molecular Speciation of Trace Metal Organic Complexes in the Pacific Ocean

    NASA Astrophysics Data System (ADS)

    Repeta, D.; Boiteau, R. M.; Bundy, R. M.; Babcock-Adams, L.

    2017-12-01

    Microbial production across approximately one third of the surface ocean is limited by extraordinarily low (picomolar) concentrations of dissolved iron, essentially all of which is complexed to strong organic ligands of unknown composition. Other biologically important trace metals (cobalt, copper, zinc, nickel) are also complexed to strong organic ligands, which again have not been extensively characterized. Nevertheless, organic ligands exert a strong influence on metal bioavailability and toxicity. For example, amendment experiments using commercially available siderophores, organic compounds synthesized by microbes to facilitate iron uptake, show these ligands can both facilitate or impede iron uptake depending on the siderophore composition and available uptake pathways. Over the past few years we have developed analytical techniques using high pressure liquid chromatography interfaced with inductively coupled plasma and electrospray ionization mass spectrometry to identify and quantify trace metal organic complexes in laboratory cultures of marine microbes and in seawater. We found siderophores to be widely distributed in the ocean, particularly in regions characterized by low iron concentrations. We also find chemically distinct complexes of copper, zinc, colbalt and nickel that we have yet to fully characterize. We will discuss some of our recent work on trace metal organic speciation in seawater and laboratory cultures, and outline future efforts to better understand the microbial cycling of trace metal organic complexes in the sea.

  20. Effect of Temperature and Sheet Temper on Isothermal Solidification Kinetics in Clad Aluminum Brazing Sheet

    NASA Astrophysics Data System (ADS)

    Benoit, Michael J.; Whitney, Mark A.; Wells, Mary A.; Winkler, Sooky

    2016-09-01

    Isothermal solidification (IS) is a phenomenon observed in clad aluminum brazing sheets, wherein the amount of liquid clad metal is reduced by penetration of the liquid clad into the core. The objective of the current investigation is to quantify the rate of IS through the use of a previously derived parameter, the Interface Rate Constant (IRC). The effect of peak temperature and initial sheet temper on IS kinetics were investigated. The results demonstrated that IS is due to the diffusion of silicon (Si) from the liquid clad layer into the solid core. Reduced amounts of liquid clad at long liquid duration times, a roughened sheet surface, and differences in resolidified clad layer morphology between sheet tempers were observed. Increased IS kinetics were predicted at higher temperatures by an IRC model as well as by experimentally determined IRC values; however, the magnitudes of these values are not in good agreement due to deficiencies in the model when applied to alloys. IS kinetics were found to be higher for sheets in the fully annealed condition when compared with work-hardened sheets, due to the influence of core grain boundaries providing high diffusivity pathways for Si diffusion, resulting in more rapid liquid clad penetration.

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

    PubMed

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

    2015-01-21

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

  2. Ibandronate metal complexes: solution behavior and antiparasitic activity.

    PubMed

    Demoro, Bruno; Rostán, Santiago; Moncada, Mauricio; Li, Zhu-Hong; Docampo, Roberto; Olea Azar, Claudio; Maya, Juan Diego; Torres, Julia; Gambino, Dinorah; Otero, Lucía

    2018-03-01

    To face the high costs of developing new drugs, researchers in both industry and academy are looking for ways to repurpose old drugs for new uses. In this sense, bisphosphonates that are clinically used for bone diseases have been studied as agents against Trypanosoma cruzi, causative parasite of Chagas disease. In this work, the development of first row transition metal complexes (M = Co 2+ , Mn 2+ , Ni 2+ ) with the bisphosphonate ibandronate (iba, H 4 iba representing the neutral form) is presented. The in-solution behavior of the systems containing iba and the selected 3d metal ions was studied by potentiometry. Mononuclear complexes [M(H x iba)] (2-x)- (x = 0-3) and [M(Hiba) 2 ] 4- together with the formation of the neutral polynuclear species [M 2 iba] and [M 3 (Hiba) 2 ] were detected for all studied systems. In the solid state, complexes of the formula [M 3 (Hiba) 2 (H 2 O) 4 ]·6H 2 O were obtained and characterized. All obtained complexes, forming [M(Hiba)] - species under the conditions of the biological studies, were more active against the amastigote form of T. cruzi than the free iba, showing no toxicity in mammalian Vero cells. In addition, the same complexes were selective inhibitors of the parasitic farnesyl diphosphate synthase (FPPS) enzyme showing poor inhibition of the human one. However, the increase of the anti-T. cruzi activity upon coordination could not be explained neither through the inhibition of TcFPPS nor through the inhibition of TcSPPS (T. cruzi solanesyl-diphosphate synthase). The ability of the obtained metal complexes of catalyzing the generation of free radical species in the parasite could explain the observed anti-T. cruzi activity.

  3. Increasing the Robustness of the Sheet Metal Forming Simulation by the Prediction of the Forming Limit Band

    NASA Astrophysics Data System (ADS)

    Banabic, D.; Vos, M.; Paraianu, L.; Jurco, P.

    2007-05-01

    The experimental research on the formability of metal sheets has shown that there is a significant dispersion of the limit strains in an area delimited by two curves: a lower curve (LFLC) and an upper one (UFLC). The region between the two curves defines the so-called Forming Limit Band (FLB). So far, this forming band has only been determined experimentally. In this paper the authors suggested a method to predict the Forming Limit Band. The proposed method is illustrated on the AA6111-T43 aluminium alloy.

  4. Pesticides Curbing Soil Fertility: Effect of Complexation of Free Metal Ions.

    PubMed

    Kaur, Sukhmanpreet; Kumar, Vijay; Chawla, Mohit; Cavallo, Luigi; Poater, Albert; Upadhyay, Niraj

    2017-01-01

    Researchers have suggested that the reason behind infertility is pernicious effect of broad spectrum pesticides on non target, beneficial microorganism of soil. Here, studying the chelating effect of selective organophosphate and carbamate pesticides with essential metal ions, at all possible combinations of three different pH (4 ± 0.05, 7 ± 0.05 and 9 ± 0.05) and three different temperatures (15 ± 0.5°C, 30 ± 0.5°C and 45 ± 0.5°C), shows very fast rate of reaction which further increases with increase of pH and temperature. Carbonyl oxygen of carbamate and phosphate oxygen of organophosphate were found to be common ligating sites among all the complexes. Formed metal complexes were found to be highly stable and water insoluble on interaction with essential metal ions in solvent medium as well as over silica. Density functional theory (DFT) calculations not only reinforced the experimental observations, but, after a wide computational conformational analysis, unraveled the nature of the high stable undesired species that consist of pesticides complexed by metal ions from the soil. All in all, apart from the direct toxicity of pesticides, the indirect effect by means of complexation of free metal ions impoverishes the soil.

  5. Pesticides Curbing Soil Fertility: Effect of Complexation of Free Metal Ions

    NASA Astrophysics Data System (ADS)

    Kaur, Sukhmanpreet; Kumar, Vijay; Chawla, Mohit; Cavallo, Luigi; Poater, Albert; Upadhyay, Niraj

    2017-07-01

    Researchers have suggested that the reason behind infertility is pernicious effect of broad spectrum pesticides on non target, beneficial microorganism of soil. Here, studying the chelating effect of selective organophosphate and carbamate pesticides with essential metal ions, at all possible combinations of three different pH (4±0.05, 7±0.05 and 9±0.05) and three different temperatures (15±0.5°C, 30±0.5°C and 45±0.5°C), shows very fast rate of reaction which further increases with increase of pH and temperature. Carbonyl oxygen of carbamate and phosphate oxygen of organophosphate were found to be common ligating sites among all the complexes. Formed metal complexes were found to be highly stable and water insoluble on interaction with essential metal ions in solvent medium as well as over silica. Density functional theory (DFT) calculations not only reinforced the experimental observations, but, after a wide computational conformational analysis, unraveled the nature of the high stable undesired species that consist of pesticides complexed by metal ions from the soil. All in all, apart from the direct toxicity of pesticides, the indirect effect by means of complexation of free metal ions impoverishes the soil.

  6. Photoactivatable metal complexes: from theory to applications in biotechnology and medicine.

    PubMed

    Smith, Nichola A; Sadler, Peter J

    2013-07-28

    This short review highlights some of the exciting new experimental and theoretical developments in the field of photoactivatable metal complexes and their applications in biotechnology and medicine. The examples chosen are based on some of the presentations at the Royal Society Discussion Meeting in June 2012, many of which are featured in more detail in other articles in this issue. This is a young field. Even the photochemistry of well-known systems such as metal-carbonyl complexes is still being elucidated. Striking are the recent developments in theory and computation (e.g. time-dependent density functional theory) and in ultrafast-pulsed radiation techniques which allow photochemical reactions to be followed and their mechanisms to be revealed on picosecond/nanosecond time scales. Not only do some metal complexes (e.g. those of Ru and Ir) possess favourable emission properties which allow functional imaging of cells and tissues (e.g. DNA interactions), but metal complexes can also provide spatially controlled photorelease of bioactive small molecules (e.g. CO and NO)--a novel strategy for site-directed therapy. This extends to cancer therapy, where metal-based precursors offer the prospect of generating excited-state drugs with new mechanisms of action that complement and augment those of current organic photosensitizers.

  7. Mechanical properties of sheet metal components with local reinforcement produced by additive manufacturing

    NASA Astrophysics Data System (ADS)

    Ünsal, Ismail; Hama-Saleh, R.; Sviridov, Alexander; Bambach, Markus; Weisheit, A.; Schleifenbaum, J. H.

    2018-05-01

    New technological challenges like electro-mobility pose an increasing demand for cost-efficient processes for the production of product variants. This demand opens the possibility to combine established die-based manufacturing methods and innovative, dieless technologies like additive manufacturing [1, 2]. In this context, additive manufacturing technologies allow for the weight-efficient local reinforcement of parts before and after forming, enabling manufacturers to produce product variants from series parts [3]. Previous work by the authors shows that the optimal shape of the reinforcing structure can be determined using sizing optimization. Sheet metal parts can then be reinforced using laser metal deposition. The material used is a pearlite-reduced, micro-alloyed steel (ZE 630). The aim of this paper is to determine the effect of the additive manufacturing process on the material behavior and the mechanical properties of the base material and the resulting composite material. The parameters of the AM process are optimized to reach similar material properties in the base material and the build-up volume. A metallographic analysis of the parts is presented, where the additive layers, the base material and also the bonding between the additive layers and the base material are analyzed. The paper shows the feasibility of the approach and details the resulting mechanical properties and performance.

  8. 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.

  9. Synthesis and antimalarial activity of metal complexes of cross-bridged tetraazamacrocyclic ligands.

    PubMed

    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

    2014-07-01

    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 Mn(2+) complex of this ligand was the most potent with IC50s of 0.127 and 0.157μM against the chloroquine-sensitive (D6) and chloroquine-resistant (W2) P. falciparum strains, respectively. In general, the dibenzyl hydrophobic ligands showed better anti-malarial 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 Mn(2+). Few of the Cu(2+) and Fe(2+) complexes also showed improvement in activity but Ni(2+), Co(2+) and Zn(2+) complexes did not show any improvement in activity upon the metal-free ligands for anti-malarial development. Published by Elsevier Ltd.

  10. Metal-metal interactions in tetrakis(diphenylphosphino)benzene-bridged dimetallic complexes and their related coordination polymers

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wang, Pei-Wei; Fox, M.A.

    1994-06-22

    Electrochemical, EPR, and spectroelectrochemical methods have been used to probe electronic coupling through a 1,2,4,5-tetrakis(diphenylphosphino)benzene bridging ligand connecting metal centers in several Ni-, Pd-, and Pt-containing dimetallic complexes. These dimetalated complexes showed weak intervalence charge transfer (IT) bands and slightly shifted redox potentials in comparison with their monometallic models. A Marcus-Hush analysis of the energies of the IT bands for the electrochemically generated mixed-valence heterodimetallic complexes (Ni{sup o}-Pd{sup II} and Ni{sup o}-Pt{sup II}, respectively) established the magnitude of intermetallic electronic coupling. The weak thermal coupling observed in these dimetalated complexes is consistent with the very low conductivities (10{sup {minus}8}-10{sup {minus}10}{omega}{supmore » -1} cm{sup {minus}1}) observed in the polymeric analogs of these complexes, namely, the newly prepared metal coordination polymers (M = Ni{sup II}, Pd{sup II}, Pt{sup II}) with 1,2,4,5-tetrakis(diphenylphosphino)benzene.« less

  11. 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.

  12. 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.

  13. Influence of Humic Acid Complexation with Metal Ions on Extracellular Electron Transfer Activity.

    PubMed

    Zhou, Shungui; Chen, Shanshan; Yuan, Yong; Lu, Qin

    2015-11-23

    Humic acids (HAs) can act as electron shuttles and mediate biogeochemical cycles, thereby influencing the transformation of nutrients and environmental pollutants. HAs commonly complex with metals in the environment, but few studies have focused on how these metals affect the roles of HAs in extracellular electron transfer (EET). In this study, HA-metal (HA-M) complexes (HA-Fe, HA-Cu, and HA-Al) were prepared and characterized. The electron shuttle capacities of HA-M complexes were experimentally evaluated through microbial Fe(III) reduction, biocurrent generation, and microbial azoreduction. The results show that the electron shuttle capacities of HAs were enhanced after complexation with Fe but were weakened when using Cu or Al. Density functional theory calculations were performed to explore the structural geometry of the HA-M complexes and revealed the best binding sites of the HAs to metals and the varied charge transfer rate constants (k). The EET activity of the HA-M complexes were in the order HA-Fe > HA-Cu > HA-Al. These findings have important implications for biogeochemical redox processes given the ubiquitous nature of both HAs and various metals in the environment.

  14. Thermal properties of highly structured composite and aluminium sheets in an aerodynamic tunnel

    NASA Astrophysics Data System (ADS)

    Kulhavy, Petr; Egert, Josef

    This article deals with the thermodynamic behaviour of heat shields - structured metal and composite plates. Experiments have been carried out in a wind tunnel with an additional heating, which simulates the heat source from engine or exhaust pipe and simultaneously the airflow generated during a car movement. The tested sheets with hexagonal structure were a standard commercial made of aluminium and a second manufactured by replication (lamination, diffusion) from glass fabric. The airflow in a parallel way along the sheets was analysed experimentally in order to determine the heat transfer efficiency between surfaces of sheets and surrounding airflow. The temperature on the sheets was chosen to observe the effects of different sheets material, various heat power and airflow velocity. During the experiment a thermal input below the sheets and airflow velocity through the tunnel have been changed. The thermal field distribution on the metal sheet is different than in case of composite sheet. For the composite material the thermal field distribution was more homogeneous. This article describe briefly also methods of obtaining real composite geometry based on scanned data and their reconstruction for using in some future numerical models.

  15. N-heterocyclic carbene metal complexes as bio-organometallic antimicrobial and anticancer drugs.

    PubMed

    Patil, Siddappa A; Patil, Shivaputra A; Patil, Renukadevi; Keri, Rangappa S; Budagumpi, Srinivasa; Balakrishna, Geetha R; Tacke, Matthias

    2015-01-01

    Late transition metal complexes that bear N-heterocyclic carbene (NHC) ligands have seen a speedy growth in their use as both, metal-based drug candidates and potentially active homogeneous catalysts in a plethora of C-C and C-N bond forming reactions. This review article focuses on the recent developments and advances in preparation and characterization of NHC-metal complexes (metal: silver, gold, copper, palladium, nickel and ruthenium) and their biomedical applications. Their design, syntheses and characterization have been reviewed and correlated to their antimicrobial and anticancer efficacies. All these initial discoveries help validate the great potential of NHC-metal derivatives as a class of effective antimicrobial and anticancer agents.

  16. A Fundamental Study of Stretch-Drawing Process of Sheet Metals : Single and Double Operations

    NASA Astrophysics Data System (ADS)

    Gotoh, Manabu; Kim, Young-soo; Yamashita, Minoru

    1998-05-01

    Fundamental and informative data of axisymmetric stretch-drawing of several sheet metals with thichness of 0.7 1.0 mm are presented especially for single and double operations. Very small radius is applied to the die-profile (or -shoulder) in all operations to induce wall-thinning by the effect of bending-under-tension, from which the name `stretch-drawing' comes. It is clearly demonstrated that deeper cups could be formed by the single and double stretch-drawings from smaller cirlcular blanks due to such wall-thinning action than in the usual deep-drawing of larger blanks. From this fact, it is emphasized that the deep-drawability of a sheet metal is not evaluated simply by the conventional LDR (=limiting drawing ratio), but the depth of the drawn cup should also be taken into account. Many experimental data about various metals and thicknesses given in this paper offer a valueable information on this process for more general use which recommends to replace the conventional deep-drawing process by the stretch-drawing process both for single and double operations. In the single stretch-drawing, it is also confirmed that a deeper cup can be produced by raising the blank-holding force at later stage of operation. Fracturing is found to occur at the middle section of the wall part or at the die-profile other than at the punch profile common in the usual deep-drawing process. Numerical simulation of the single stretch-drawing process is also performed by use of DYNA-3D code to confirm that a satisfactory prediction especially in the depth of the drawn-cup can be done at least in a practical sense, although this kind of numerical analysis is very difficult because of the severity or localization of deformation around the die profile. The drawn cup of SUS304 among others fractures in a couple of weeks after the operation due to the residual circumferential tensile stress, whereas that of SUS304L does not. In the double stretch-drawing, it is confirmed that very deeper

  17. 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.

  18. The preparation and use of metal salen complexes derived from cyclobutane diamine

    NASA Astrophysics Data System (ADS)

    Patil, Smita

    The helix is an important chiral motif in nature, there is increasing development in field of helical transition metal complexes and related supramolecular structures. Hence, the goals of this work are to apply the principles of helicity in order to produce metal complexes with predictable molecular shapes and to study their properties as asymmetric catalysts. Computational studies suggest that the (1R,2 R)-cyclobutyldiamine unit can produce highly twisted salen complexes with a large energy barrier between the M and P helical forms. To test this prediction, the tartrate salt of (1R,2R)-cyclobutyldiamine was synthesized and condensed with a series of saliclaldehydes to produce novel salen ligands. The salicylaldehydes chosen have extended phenanthryl or benz[a]anthryl sidearms to encourage formation of helical coordination complexes. These ligands were metallated with zinc, iron and manganese salts to produce salen metal complexes which were characterized by NMR analysis, high-resolution mass spectrometry, and IR spectroscopy. A second ligand type, neutral bis(pyridine-imine) has also been synthesized from (1R,2R)-cyclobutyldiamine and quinolylaldehydes. The synthesis of bis(pyridine-imine) ligands was conducted using greener method, solvent assisted grinding. These ligands, in-situ with nickel metal salts, showed good catalytic activity for asymmetric Diels-Alder reactions. The third ligand type studied was chiral acid-functionalized Schiff-base ligands. These were synthesized by the condensation of 3-formyl-5-methyl salicylic acid and (1R,2R)-cyclobutyldiamine. With this type of ligand, there is possibility of producing both mono and dinuclear metal complexes. In our studies, we were only able to synthesize mononuclear complexs. These were tested as catalysts for asymmetric direct Mannich-type reaction, but were found to be ineffective.

  19. Sense and readability: participant information sheets for research studies.

    PubMed

    Ennis, Liam; Wykes, Til

    2016-02-01

    Informed consent in research is partly achieved through the use of information sheets. There is a perception however that these information sheets are long and complex. The recommended reading level for patient information is grade 6, or 11-12 years old. To investigate whether the readability of participant information sheets has changed over time, whether particular study characteristics are related to poorer readability and whether readability and other study characteristics are related to successful study recruitment. Method: We obtained 522 information sheets from the UK National Institute for Health Research Clinical Research Network: Mental Health portfolio database and study principal investigators. Readability was assessed with the Flesch reading index and the Grade level test. Information sheets increased in length over the study period. The mean grade level across all information sheets was 9.8, or 15-16 years old. A high level of patient involvement was associated with more recruitment success and studies involving pharmaceutical or device interventions were the least successful. The complexity of information sheets had little bearing on successful recruitment. Information sheets are far more complex than the recommended reading level of grade 6 for patient information. The disparity may be exacerbated by an increasing focus on legal content. Researchers would benefit from clear guidance from ethics committees on writing succinctly and accessibly and how to balance the competing legal issues with the ability of participants to understand what a study entails. © The Royal College of Psychiatrists 2016.

  20. Sense and readability: participant information sheets for research studies

    PubMed Central

    Ennis, Liam; Wykes, Til

    2016-01-01

    Background Informed consent in research is partly achieved through the use of information sheets. There is a perception however that these information sheets are long and complex. The recommended reading level for patient information is grade 6, or 11–12 years old. Aims To investigate whether the readability of participant information sheets has changed over time, whether particular study characteristics are related to poorer readability and whether readability and other study characteristics are related to successful study recruitment. Method We obtained 522 information sheets from the UK National Institute for Health Research Clinical Research Network: Mental Health portfolio database and study principal investigators. Readability was assessed with the Flesch reading index and the Grade level test. Results Information sheets increased in length over the study period. The mean grade level across all information sheets was 9.8, or 15–16 years old. A high level of patient involvement was associated with more recruitment success and studies involving pharmaceutical or device interventions were the least successful. The complexity of information sheets had little bearing on successful recruitment. Conclusions Information sheets are far more complex than the recommended reading level of grade 6 for patient information. The disparity may be exacerbated by an increasing focus on legal content. Researchers would benefit from clear guidance from ethics committees on writing succinctly and accessibly and how to balance the competing legal issues with the ability of participants to understand what a study entails. PMID:26382948

  1. Resin infusion of layered metal/composite hybrid and resulting metal/composite hybrid laminate

    NASA Technical Reports Server (NTRS)

    Cano, Roberto J. (Inventor); Grimsley, Brian W. (Inventor); Weiser, Erik S. (Inventor); Jensen, Brian J. (Inventor)

    2009-01-01

    A method of fabricating a metal/composite hybrid laminate is provided. One or more layered arrangements are stacked on a solid base to form a layered structure. Each layered arrangement is defined by a fibrous material and a perforated metal sheet. A resin in its liquid state is introduced along a portion of the layered structure while a differential pressure is applied across the laminate structure until the resin permeates the fibrous material of each layered arrangement and fills perforations in each perforated metal sheet. The resin is cured thereby yielding a metal/composite hybrid laminate.

  2. Graphene-supported metal oxide monolith

    DOEpatents

    Worsley, Marcus A.; Baumann, Theodore F.; Biener, Juergen; Biener, Monika A.; Wang, Yinmin; Ye, Jianchao; Tylski, Elijah

    2017-01-10

    A composition comprising at least one graphene-supported metal oxide monolith, said monolith comprising a three-dimensional structure of graphene sheets crosslinked by covalent carbon bonds, wherein the graphene sheets are coated by at least one metal oxide such as iron oxide or titanium oxide. Also provided is an electrode comprising the aforementioned graphene-supported metal oxide monolith, wherein the electrode can be substantially free of any carbon-black and substantially free of any binder.

  3. Reductive dechlorination of trichloroethene mediated by humic-metal complexes

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    O`Loughlin, E.J.; Burris, D.R.; Delcomyn, C.A.

    1999-04-01

    Experiments were conducted to determine if transition metal-humic acid complexes can act as e{sup {minus}} transfer mediators in the reductive dechlorination of trichloroethene (TCE) using Ti(III) citrate as the bulk reductant. In the presence of Ni-Aldrich humic acid (AHA) complexes, TCE reduction was rapid, with complete removal of TCE in less than 23 h. Cu-AHA complexes were less effective as e{sup {minus}} mediators than Ni-AHA complexes; only 60% of TCE was reduced after 150 h. Partially dechlorinated intermediates were observed during TCE reduction; however, they were transitory, and at no time accounted for more than 2% of the initial TCEmore » mass on a mole C basis. Ethane and ethene were the primary end products of TCE reduction; however, a suite of other non-chlorinated hydrocarbons consisting of methane and C{sub 3} to C{sub 6} alkanes and alkenes were also observed. The results suggest that humic-metal complexes may represent a previously unrecognized class of electron mediators in natural environments.« less

  4. 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.

  5. 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.

  6. 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.

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

    PubMed

    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 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 d(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 O2 adsorption energy for enhancing the ORR activity of transition metal macrocyclic complex catalysts.

  8. Infrared Multiple-Photon Dissociation spectroscopy of group II metal complexes with salicylate

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ryan P. Dain; Gary Gresham; Gary S. Groenewold

    2011-07-01

    Ion-trap tandem mass spectrometry with collision-induced dissociation, and the combination of infrared multiple-photon dissociation (IRMPD) spectroscopy and density functional theory (DFT) calculations were used to characterize singly-charged, 1:1 complexes of Ca2+, Sr2+ and Ba2+ with salicylate. For each metal-salicylate complex, the CID pathways are: (a) elimination of CO2 and (b) formation of [MOH]+ where M=Ca2+, Sr2+ or Ba2+. DFT calculations predict three minima for the cation-salicylate complexes which differ in the mode of metal binding. In the first, the metal ion is coordinated by O atoms of the (neutral) phenol and carboxylate groups of salicylate. In the second, the cationmore » is coordinated by phenoxide and (neutral) carboxylic acid groups. The third mode involves coordination by the carboxylate group alone. The infrared spectrum for the metal-salicylate complexes contains a number of absorptions between 1000 – 1650 cm-1, and the best correlation between theoretical and experimental spectra for the structure that features coordination of the metal ion by phenoxide and the carbonyl group of the carboxylic acid group, consistent with calculated energies for the respective species.« less

  9. Evaluation of the tratment of metal-EDTA complexes using Ti0{sub 2} photocatalysis

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Madden, T.; Datyte, A.K.; Prairie, M.R.

    1996-03-01

    This study has demonstrated the feasibility of TiO{sub 2} photocatalysis to treat EDTA and several metal-EDTA complexes that can be found in industrial wastewaters. For the EDTA complexes of metals capable of photodeposition, such as Cu and Pb, certain reaction conditions were shown to facilitate the simultaneous complex degradation and photodeposition of these metals onto the catalyst. With metals that do not easily photodeposit, such as Ni and Cd, it is shown that the complex degradation is still facilitated, and can enhance other metals removal processes after photocatalytic treatment. Because the treatment of these metal-EDTA complexes typically requires special measures,more » there may exist situations where TiO{sub 2} photocatalysis could actually be the preferred method of treatment. However, its use should be compared economically to other more established advanced oxidation technologies. This necessity is demonstrated in the economic comparison to ozone treatment for EDTA degradation alone, where ozone treatment appears to be the clear choice in this application.« less

  10. 3D finite element modelling of sheet metal blanking process

    NASA Astrophysics Data System (ADS)

    Bohdal, Lukasz; Kukielka, Leon; Chodor, Jaroslaw; Kulakowska, Agnieszka; Patyk, Radoslaw; Kaldunski, Pawel

    2018-05-01

    The shearing process such as the blanking of sheet metals has been used often to prepare workpieces for subsequent forming operations. The use of FEM simulation is increasing for investigation and optimizing the blanking process. In the current literature a blanking FEM simulations for the limited capability and large computational cost of the three dimensional (3D) analysis has been largely limited to two dimensional (2D) plane axis-symmetry problems. However, a significant progress in modelling which takes into account the influence of real material (e.g. microstructure of the material), physical and technological conditions can be obtained by using 3D numerical analysis methods in this area. The objective of this paper is to present 3D finite element analysis of the ductile fracture, strain distribution and stress in blanking process with the assumption geometrical and physical nonlinearities. The physical, mathematical and computer model of the process are elaborated. Dynamic effects, mechanical coupling, constitutive damage law and contact friction are taken into account. The application in ANSYS/LS-DYNA program is elaborated. The effect of the main process parameter a blanking clearance on the deformation of 1018 steel and quality of the blank's sheared edge is analyzed. The results of computer simulations can be used to forecasting quality of the final parts optimization.

  11. 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…

  12. Simultaneous separation of inorganic anions and metal-citrate complexes on a zwitterionic stationary phase with on-column complexation.

    PubMed

    Nesterenko, Ekaterina P; Nesterenko, Pavel N; Paull, Brett

    2008-12-05

    The retention and separation selectivity of inorganic anions and on-column derivatised negatively charged citrate or oxalate metal complexes on reversed-phase stationary phases dynamically coated with N-(dodecyl-N,N-dimethylammonio)undecanoate (DDMAU) has been investigated. The retention mechanism for the metal-citrate complexes was predominantly anion exchange, although the amphoteric/zwitterionic nature of the stationary phase coating undoubtedly also contributed to the unusual separation selectivity shown. A mixture of 10 inorganic anions and metal cations was achieved using a 20 cm monolithic DDMAU modified column and a 1 mM citrate eluent, pH 4.0, flow rate equal to 0.8 mL/min. Selectivity was found to be strongly pH dependent, allowing additional scope for manipulation of solute retention, and thus application to complex samples. This is illustrated with the analysis of an acidic mine drainage sample with a range of inorganic anions and transition metal cations, varying significantly in their concentrations levels.

  13. 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…

  14. Chemistry in acetone complexes of metal dications: a remarkable ethylene production pathway.

    PubMed

    Wu, Jianhua; Liu, Dan; Zhou, Jian-Ge; Hagelberg, Frank; Park, Sung Soo; Shvartsburg, Alexandre A

    2007-06-07

    Electrospray ionization can generate microsolvated multiply charged metal ions for various metals and ligands, allowing exploration of chemistry within such clusters. The finite size of these systems permits comparing experimental results with accurate calculations, creating a natural laboratory to research ion solvation. Mass spectrometry has provided much insight into the stability and dissociation of ligated metal cations. While solvated singly charged ions tend to shrink by ligand evaporation, solvated polycations below a certain size exhibit charge reduction and/or ligand fragmentation due to organometallic reactions. Here we investigate the acetone complexes of representative divalent metals (Ca, Mn, Co, Ni, and Cu), comparing the results of collision-induced dissociation with the predictions of density functional theory. As for other solvated dications, channels involving proton or electron transfer compete with ligand loss and become dominant for smaller complexes. The heterolytic C-C bond cleavage is common, like in DMSO and acetonitrile complexes. Of primary interest is the unanticipated neutral ethylene loss, found for all metals studied except Cu and particularly intense for Ca and Mn. We focus on understanding that process in the context of competing dissociation pathways, as a function of metal identity and number of ligands. According to first-principles modeling, ethylene elimination proceeds along a complex path involving two intermediates. These results suggest that chemistry in microsolvated multiply charged ions may still hold major surprises.

  15. Metal-organic complexes in geochemical processes: Estimation of standard partial molal thermodynamic properties of aqueous complexes between metal cations and monovalent organic acid ligands at high pressures and temperatures

    NASA Astrophysics Data System (ADS)

    Shock, Everetr L.; Koretsky, Carla M.

    1995-04-01

    Regression of standard state equilibrium constants with the revised Helgeson-Kirkham-Flowers (HKF) equation of state allows evaluation of standard partial molal entropies ( overlineSo) of aqueous metal-organic complexes involving monovalent organic acid ligands. These values of overlineSo provide the basis for correlations that can be used, together with correlation algorithms among standard partial molal properties of aqueous complexes and equation-of-state parameters, to estimate thermodynamic properties including equilibrium constants for complexes between aqueous metals and several monovalent organic acid ligands at the elevated pressures and temperatures of many geochemical processes which involve aqueous solutions. Data, parameters, and estimates are given for 270 formate, propanoate, n-butanoate, n-pentanoate, glycolate, lactate, glycinate, and alanate complexes, and a consistent algorithm is provided for making other estimates. Standard partial molal entropies of association ( Δ -Sro) for metal-monovalent organic acid ligand complexes fall into at least two groups dependent upon the type of functional groups present in the ligand. It is shown that isothermal correlations among equilibrium constants for complex formation are consistent with one another and with similar correlations for inorganic metal-ligand complexes. Additional correlations allow estimates of standard partial molal Gibbs free energies of association at 25°C and 1 bar which can be used in cases where no experimentally derived values are available.

  16. 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.

  17. Ga metal nanoparticle-GaAs quantum molecule complexes for Terahertz generation.

    PubMed

    Bietti, Sergio; Basso Basset, Francesco; Scarpellini, David; Fedorov, Alexey; Ballabio, Andrea; Esposito, Luca; Elborg, Martin; Kuroda, Takashi; Nemcsics, Akos; Toth, Lajos; Manzoni, Cristian; Vozzi, Caterina; Sanguinetti, Stefano

    2018-06-18

    A hybrid metal-semiconductor nanosystem for the generation of THz radiation, based on the fabrication of GaAs quantum molecules-Ga metal nanoparticles complexes through a self assembly approach, is proposed. The role of the growth parameters, the substrate temperature, the Ga and As flux during the quantum dot molecule fabrication and the metal nanoparticle alignment is discussed. The tuning of the relative positioning of quantum dot molecules and metal nanoparticles is obtained through the careful control of Ga droplet nucleation sites via Ga surface diffusion. The electronic structure of a typical quantum dot molecule was evaluated on the base of the morphological characterizations performed by Atomic Force Microscopy and cross sectional Scanning Electron Microscopy, and the predicted results confirmed by micro-photoluminescence experiments, showing that the Ga metal nanoparticle-GaAs quantum molecule complexes are suitable for terahertz generation from intraband transition. . © 2018 IOP Publishing Ltd.

  18. 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

  19. Photoinduced energy transfer in transition metal complex oligomers

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    NONE

    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,more » 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.« less

  20. Photoinduced energy transfer in transition metal complex oligomers

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    NONE

    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,more » 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.« less

  1. The QSAR study of flavonoid-metal complexes scavenging rad OH free radical

    NASA Astrophysics Data System (ADS)

    Wang, Bo-chu; Qian, Jun-zhen; Fan, Ying; Tan, Jun

    2014-10-01

    Flavonoid-metal complexes have antioxidant activities. However, quantitative structure-activity relationships (QSAR) of flavonoid-metal complexes and their antioxidant activities has still not been tackled. On the basis of 21 structures of flavonoid-metal complexes and their antioxidant activities for scavenging rad OH free radical, we optimised their structures using Gaussian 03 software package and we subsequently calculated and chose 18 quantum chemistry descriptors such as dipole, charge and energy. Then we chose several quantum chemistry descriptors that are very important to the IC50 of flavonoid-metal complexes for scavenging rad OH free radical through method of stepwise linear regression, Meanwhile we obtained 4 new variables through the principal component analysis. Finally, we built the QSAR models based on those important quantum chemistry descriptors and the 4 new variables as the independent variables and the IC50 as the dependent variable using an Artificial Neural Network (ANN), and we validated the two models using experimental data. These results show that the two models in this paper are reliable and predictable.

  2. The pressure tunning Raman and IR spectral studies on the multinuclear metal carbyne complexes

    NASA Astrophysics Data System (ADS)

    Xu, Zhenhua; Butler, Ian S.; Mayr, Andreas

    2005-03-01

    The Raman and infrared (IR) spectra of four tungsten metal carbyne complexes I, II, IV and V [Cl(CO) 2(L)W tbnd CC 6H 4sbnd (C tbnd CC 6H 4) nsbnd N tbnd C sbnd ] 2M (L = TMEDA, n = 0, M = PdI 2 or ReCl(CO) 3; L = DPPE, n = 1, M = PdI 2 or ReCl(CO) 3) were studied at high external pressure. Their pressure-induced phase transitions were observed near 20 kbar (complexes I), 15 kbar (complexes II), 25 kbar (complex IV) and 30 kbar (complex V). The pressure-induced phase transition likely is first order in complex I and the pressure-induced phase transitions of complexes II, IV and V are mostly second order. The pressure sensitivities d ν/d p of ν(W tbnd C) are high in the low-pressure phase area and very low in the high-pressure phase area due to the pressure strengthening π back-bonding from metal W to π * orbital of C tbnd O in fragment Cl(CO) 2(L)W tbnd C. The pressure strengthening metal π back-bonding from metal Re or Pd to π * orbital of C tbnd O or C tbnd N also happened to both of central metal centers of NCPd(I 2)CN in complex I and NCReCl(CO) 3CN in complex II.

  3. 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.

  4. Molecular modelling, spectroscopic characterization and biological studies of tetraazamacrocyclic metal complexes

    NASA Astrophysics Data System (ADS)

    Rathi, Parveen; Sharma, Kavita; Singh, Dharam Pal

    2014-09-01

    Macrocyclic complexes of the type [MLX]X2; where L is (C30H28N4), a macrocyclic ligand, M = Cr(III) and Fe(III) and X = Cl-, CH3COO- or NO3-, have been synthesized by template condensation reaction of 1,8-diaminonaphthalene and acetylacetone in the presence of trivalent metal salts in a methanolic medium. The complexes have been formulated as [MLX]X2 due to 1:2 electrolytic nature of these complexes. The complexes have been characterized with the help of elemental analyses, molar conductance measurements, magnetic susceptibility measurements, electronic, infrared, far infrared, Mass spectral studies and molecular modelling. Molecular weight of these complexes indicates their monomeric nature. On the basis of all these studies, a five coordinated square pyramidal geometry has been proposed for all these complexes. These metal complexes have also been screened for their in vitro antimicrobial activities.

  5. Zwitterionic metal carboxylate complexes: In solid state

    NASA Astrophysics Data System (ADS)

    Nath, Bhaskar; Kalita, Dipjyoti; Baruah, Jubaraj B.

    2012-07-01

    A flexible dicarboxylic acid having composition [(CH(o-C5H4N)(p-C6H4OCH2CO2H)2] derived from corresponding bis-phenol reacts with various metal(II) acetates such as manganese(II), cobalt(II) and nickel(II) acetate leads to zwtterionic complexes with compositions [CH(o-C5H4N)(p-C6H4OCH2CO2){p-C6H4OCH2CO2M(H2O)5}].6H2O (where M = Mn, Co, Ni). The complexes are characterised by X-ray crystallography. These complexes have chiral center due to unsymmetric structure conferred to the ligand through coordination at only one carboxylate group of the ligand. In solid state these complexes are racemic.

  6. Infrared multiple-photon dissociation spectroscopy of group II metal complexes with salicylate.

    PubMed

    Dain, Ryan P; Gresham, Gary; Groenewold, Gary S; Steill, Jeffrey D; Oomens, Jos; van Stipdonk, Michael J

    2011-07-15

    Ion trap tandem mass spectrometry with collision-induced dissociation, and the combination of infrared multiple-photon dissociation (IRMPD) spectroscopy and density functional theory (DFT) calculations, were used to characterize singly charged, 1:1 complexes of Ca(2+), Sr(2+) and Ba(2+) with salicylate. For each metal-salicylate complex, the CID pathways are: (a) elimination of CO(2) and (b) formation of [MOH](+) where M = Ca(2+), Sr(2+) or Ba(2+). DFT calculations predict three minima for the cation-salicylate complexes which differ in the mode of metal binding. In the first, the metal ion is coordinated by O atoms of the (neutral) phenol and carboxylate groups of salicylate. In the second, the cation is coordinated by phenoxide and (neutral) carboxylic acid groups. The third mode involves coordination by the carboxylate group alone. The infrared spectrum for the metal-salicylate complexes contains a number of absorptions between 1000 and 1650 cm(-1), and the best correlation between theoretical and experimental spectra is found for the structure that features coordination of the metal ion by phenoxide and the carbonyl O of the carboxylic acid group, consistent with the calculated energies for the respective species. Copyright © 2011 John Wiley & Sons, Ltd.

  7. Metal complexes of curcumin for cellular imaging, targeting, and photoinduced anticancer activity.

    PubMed

    Banerjee, Samya; Chakravarty, Akhil R

    2015-07-21

    Curcumin is a polyphenolic species. As an active ingredient of turmeric, it is well-known for its traditional medicinal properties. The therapeutic values include antioxidant, anti-inflammatory, antiseptic, and anticancer activity with the last being primarily due to inhibition of the transcription factor NF-κB besides affecting several biological pathways to arrest tumor growth and its progression. Curcumin with all these positive qualities has only remained a potential candidate for cancer treatment over the years without seeing any proper usage because of its hydrolytic instability involving the diketo moiety in a cellular medium and its poor bioavailability. The situation has changed considerably in recent years with the observation that curcumin in monoanionic form could be stabilized on binding to a metal ion. The reports from our group and other groups have shown that curcumin in the metal-bound form retains its therapeutic potential. This has opened up new avenues to develop curcumin-based metal complexes as anticancer agents. Zinc(II) complexes of curcumin are shown to be stable in a cellular medium. They display moderate cytotoxicity against prostate cancer and neuroblastoma cell lines. A similar stabilization and cytotoxic effect is reported for (arene)ruthenium(II) complexes of curcumin against a variety of cell lines. The half-sandwich 1,3,5-triaza-7-phosphatricyclo-[3.3.1.1]decane (RAPTA)-type ruthenium(II) complexes of curcumin are shown to be promising cytotoxic agents with low micromolar concentrations for a series of cancer cell lines. In a different approach, cobalt(III) complexes of curcumin are used for its cellular delivery in hypoxic tumor cells using intracellular agents that reduce the metal and release curcumin as a cytotoxin. Utilizing the photophysical and photochemical properties of the curcumin dye, we have designed and synthesized photoactive curcumin metal complexes that are used for cellular imaging by fluorescence microscopy and

  8. 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.

  9. 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)

  10. Quantitative Interpretation of Multifrequency Multimode EPR Spectra of Metal Containing Proteins, Enzymes, and Biomimetic Complexes.

    PubMed

    Petasis, Doros T; Hendrich, Michael P

    2015-01-01

    Electron paramagnetic resonance (EPR) spectroscopy has long been a primary method for characterization of paramagnetic centers in materials and biological complexes. Transition metals in biological complexes have valence d-orbitals that largely define the chemistry of the metal centers. EPR spectra are distinctive for metal type, oxidation state, protein environment, substrates, and inhibitors. The study of many metal centers in proteins, enzymes, and biomimetic complexes has led to the development of a systematic methodology for quantitative interpretation of EPR spectra from a wide array of metal containing complexes. The methodology is now contained in the computer program SpinCount. SpinCount allows simulation of EPR spectra from any sample containing multiple species composed of one or two metals in any spin state. The simulations are quantitative, thus allowing determination of all species concentrations in a sample directly from spectra. This chapter will focus on applications to transition metals in biological systems using EPR spectra from multiple microwave frequencies and modes. © 2015 Elsevier Inc. All rights reserved.

  11. Ternary metal-rich sulfide with a layered structure

    DOEpatents

    Franzen, Hugo F.; Yao, Xiaoqiang

    1993-08-17

    A ternary Nb-Ta-S compound is provided having the atomic formula, Nb.sub.1.72 Ta.sub.3.28 S.sub.2, and exhibiting a layered structure in the sequence S-M3-M2-M1-M2-M3-S wherein S represents sulfur layers and M1, M2, and M3 represent Nb/Ta mixed metal layers. This sequence generates seven sheets stacked along the [001] direction of an approximate body centered cubic crystal structure with relatively weak sulfur-to-sulfur van der Waals type interactions between adjacent sulfur sheets and metal-to-metal bonding within and between adjacent mixed metal sheets.

  12. Quantification of trace metals in water using complexation and filter concentration.

    PubMed

    Dolgin, Bella; Bulatov, Valery; Japarov, Julia; Elish, Eyal; Edri, Elad; Schechter, Israel

    2010-06-15

    Various metals undergo complexation with organic reagents, resulting in colored products. In practice, their molar absorptivities allow for quantification in the ppm range. However, a proper pre-concentration of the colored complex on paper filter lowers the quantification limit to the low ppb range. In this study, several pre-concentration techniques have been examined and compared: filtering the already complexed mixture, complexation on filter, and dipping of dye-covered filter in solution. The best quantification has been based on the ratio of filter reflectance at a certain wavelength to that at zero metal concentration. The studied complex formations (Ni ions with TAN and Cd ions with PAN) involve production of nanoparticle suspensions, which are associated with complicated kinetics. The kinetics of the complexation of Ni ions with TAN has been investigated and optimum timing could be found. Kinetic optimization in regard to some interferences has also been suggested.

  13. Explicit and implicit springback simulation in sheet metal forming using fully coupled ductile damage and distortional hardening model

    NASA Astrophysics Data System (ADS)

    Yetna n'jock, M.; Houssem, B.; Labergere, C.; Saanouni, K.; Zhenming, Y.

    2018-05-01

    The springback is an important phenomenon which accompanies the forming of metallic sheets especially for high strength materials. A quantitative prediction of springback becomes very important for newly developed material with high mechanical characteristics. In this work, a numerical methodology is developed to quantify this undesirable phenomenon. This methodoly is based on the use of both explicit and implicit finite element solvers of Abaqus®. The most important ingredient of this methodology consists on the use of highly predictive mechanical model. A thermodynamically-consistent, non-associative and fully anisotropic elastoplastic constitutive model strongly coupled with isotropic ductile damage and accounting for distortional hardening is then used. An algorithm for local integration of the complete set of the constitutive equations is developed. This algorithm considers the rotated frame formulation (RFF) to ensure the incremental objectivity of the model in the framework of finite strains. This algorithm is implemented in both explicit (Abaqus/Explicit®) and implicit (Abaqus/Standard®) solvers of Abaqus® through the users routine VUMAT and UMAT respectively. The implicit solver of Abaqus® has been used to study spingback as it is generally a quasi-static unloading. In order to compare the methods `efficiency, the explicit method (Dynamic Relaxation Method) proposed by Rayleigh has been also used for springback prediction. The results obtained within U draw/bending benchmark are studied, discussed and compared with experimental results as reference. Finally, the purpose of this work is to evaluate the reliability of different methods predict efficiently springback in sheet metal forming.

  14. New technique for heterogeneous vapor-phase synthesis of nanostructured metal layers from low-dimensional volatile metal complexes

    NASA Astrophysics Data System (ADS)

    Badalyan, A. M.; Bakhturova, L. F.; Kaichev, V. V.; Polyakov, O. V.; Pchelyakov, O. P.; Smirnov, G. I.

    2011-09-01

    A new technique for depositing thin nanostructured layers on semiconductor and insulating substrates that is based on heterogeneous gas-phase synthesis from low-dimensional volatile metal complexes is suggested and tried out. Thin nanostructured copper layers are deposited on silicon and quartz substrates from low-dimensional formate complexes using a combined synthesis-mass transport process. It is found that copper in layers thus deposited is largely in a metal state (Cu0) and has the form of closely packed nanograins with a characteristic structure.

  15. 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

  16. Metal ion influence on eumelanin fluorescence and structure.

    PubMed

    Sutter, Jens-Uwe; Birch, David J S

    2014-04-10

    Melanin has long been thought to have an unworkably weak and complex fluorescence, but here we study its intrinsic fluorescence in order to demonstrate how metal ions can be used to control the rate of formation, constituents and structure of eumelanin formed from the well-known laboratory auto-oxidation of 3,4-dihydroxy-L-phenylalanine (L-DOPA). The effect on eumelanin absorption and fluorescence of a range of solvated metal ions is reported including Cu, Zn, Ni, Na and K. Monovalent cations and Zn have little effect, but the effect of transition metal cations can be considerable. For example, at pH 10, copper ions are shown to accelerate the onset of eumelanin formation, but not the rate of formation once it commences, and simplify the usual complex structure and intrinsic fluorescence of eumelanin in a way that is consistent with an increased abundance of 5,5-dihydroxyindole-2-carboxylic acid (DHICA). The presence of a dominant 6 ns fluorescence decay time at 480 nm, when excited at 450 nm describes a distinct photophysical species, which we tentatively assign to small oligomers. Copper is well-known to normally quench fluorescence, but increasing amounts of copper surprisingly leads to an increase in the fluorescence decay time of eumelanin, while reducing the fluorescence intensity, suggesting copper modification of the excited state. Such results have bearing on diverse areas. The most accepted morphology for melanin is that of a graphite-like sheet structure, and one which readily binds metal ions, an interaction that is thought to have an important, though as yet unclear bearing on several areas of medicine including neurology. There is also increasing interest in bio-mimicry by preparing and labelling sheet structures with metal ions for new electronic and photonic materials.

  17. Metal ion influence on eumelanin fluorescence and structure

    NASA Astrophysics Data System (ADS)

    Sutter, Jens-Uwe; Birch, David J. S.

    2014-06-01

    Melanin has long been thought to have an unworkably weak and complex fluorescence, but here we study its intrinsic fluorescence in order to demonstrate how metal ions can be used to control the rate of formation, constituents and structure of eumelanin formed from the well-known laboratory auto-oxidation of 3,4-dihydroxy-L-phenylalanine (L-DOPA). The effect on eumelanin absorption and fluorescence of a range of solvated metal ions is reported including Cu, Zn, Ni, Na and K. Monovalent cations and Zn have little effect, but the effect of transition metal cations can be considerable. For example, at pH 10, copper ions are shown to accelerate the onset of eumelanin formation, but not the rate of formation once it commences, and simplify the usual complex structure and intrinsic fluorescence of eumelanin in a way that is consistent with an increased abundance of 5,5-dihydroxyindole-2-carboxylic acid (DHICA). The presence of a dominant 6 ns fluorescence decay time at 480 nm, when excited at 450 nm describes a distinct photophysical species, which we tentatively assign to small oligomers. Copper is well-known to normally quench fluorescence, but increasing amounts of copper surprisingly leads to an increase in the fluorescence decay time of eumelanin, while reducing the fluorescence intensity, suggesting copper modification of the excited state. Such results have bearing on diverse areas. The most accepted morphology for melanin is that of a graphite-like sheet structure, and one which readily binds metal ions, an interaction that is thought to have an important, though as yet unclear bearing on several areas of medicine including neurology. There is also increasing interest in bio-mimicry by preparing and labelling sheet structures with metal ions for new electronic and photonic materials.

  18. 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.

  19. Analysis of fracture in sheet bending and roll forming

    NASA Astrophysics Data System (ADS)

    Deole, Aditya D.; Barnett, Matthew; Weiss, Matthias

    2018-05-01

    The bending limit or minimum bending radius of sheet metal is conventionally measured in a wiping (swing arm) or in a vee bend test and reported as the minimum radius of the tool over which the sheet can be bent without fracture. Frequently the material kinks while bending so that the actual inner bend radius of the sheet metal is smaller than the tool radius giving rise to inaccuracy in these methods. It has been shown in the previous studies that conventional bend test methods may under-estimate formability in bending dominated processes such as roll forming. A new test procedure is proposed here to improve understanding and measurement of fracture in bending and roll forming. In this study, conventional wiping test and vee bend test have been performed on martensitic steel to determine the minimum bend radius. In addition, the vee bend test is performed in an Erichsen sheet metal tester equipped with the GOM Aramis system to enable strain measurement on the outer surface during bending. The strain measurement before the onset of fracture is then used to determine the minimum bend radius. To compare this result with a technological process, a vee channel is roll formed and in-situ strain measurement carried out with the Vialux Autogrid system. The strain distribution at fracture in the roll forming process is compared with that predicted by the conventional bending tests and by the improved process. It is shown that for this forming operation and material, the improved procedure gives a more accurate prediction of fracture.

  20. Density functional theory study on Herzberg-Teller contribution in Raman scattering from 4-aminothiophenol-metal complex and metal-4-aminothiophenol-metal junction

    NASA Astrophysics Data System (ADS)

    Liu, Shasha; Zhao, Xiuming; Li, Yuanzuo; Zhao, Xiaohong; Chen, Maodu

    2009-06-01

    Density functional theory (DFT) and time-dependent DFT calculations have been performed to investigate the Raman scattering spectra of metal-molecule complex and metal-molecule-metal junction architectures interconnected with 4-aminothiophenol (PATP) molecule. The simulated profiles of normal Raman scattering (NRS) spectra for the two complexes (Ag2-PATP and PATP-Au2) and the two junctions (Ag2-PATP-Au2 and Au2-PATP-Ag2) are similar to each other, but exhibit obviously different Raman intensities. Due to the lager static polarizabilities of the two junctions, which directly influence the ground state chemical enhancement in NRS spectra, the calculated normal Raman intensities of them are stronger than those of two complexes by the factor of 102. We calculate preresonance Raman scattering (RRS) spectra with incident light at 1064 nm, which is much lower than the S1 electronic transition energy of complexes and junctions. Ag2-PATP-Au2 and Au2-PATP-Ag2 junctions yield higher Raman intensities than those of Ag2-PATP and PATP-Au2 complexes, especially for b2 modes. This effect is mainly attributed to charge transfer (CT) between the metal gap and the PAPT molecule which results in the occurrence of CT resonance enhancement. The calculated pre-RRS spectra strongly depend on the electronic transition state produced by new structures. With excitation at 514.5 nm, the calculated pre-RRS spectra of two complexes and two junctions are stronger than those of with excitation at 1064 nm. A charge difference densities methodology has been used to visually describe chemical enhancement mechanism of RRS spectrum. This methodology aims at visualizing intermolecular CT which provides direct evidence of the Herzberg-Teller mechanism.

  1. 75 FR 76037 - General Motors Corporation Grand Rapids Metal Center Metal Fabricating Division Including On-Site...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-12-07

    ... Corporation Grand Rapids Metal Center Metal Fabricating Division Including On-Site Leased Workers From... Corporation, Grand Rapids Metal Center, Metal Fabricating Division, including on- site leased workers from... of metal stampings and sub- assembled metal sheet components. The company reports that workers leased...

  2. The molecular structure and vibrational spectra of corrolazine metal complexes (CzM) by density functional theory

    NASA Astrophysics Data System (ADS)

    Wang, Hongming; Yang, Chuanlu; Zhang, Zhihong; Wang, Meishan; Han, Keli

    2006-06-01

    The ground-state geometries, electronic structures and vibrational frequencies of metal corrolazine complexes, CzM (M = Mn, Co, Ni and Fe) have been studied using B3LYP/6-311g(d) method. The molecular geometries are sensitive to the species of the metal, and the bond length of the M sbnd N is increase with the metal atom radii. The ground-state electronic structures indicate that there are strong interactions between d of the metal fragments and the corrolazine fragments. The calculations also indicate that the CzNi is the stabilest among the four metal corrolazine complexes. Vibrational frequencies of these metal corrolazine complexes were also calculated and were assigned to the local coordinates of the corrolazine ring, which reveals the some common feature of the molecular vibrations of the metal corrolazine complexes as four-coordination metallocorrolazines.

  3. Ylide Ligands as Building Blocks for Bioactive Group 11 Metal Complexes.

    PubMed

    Gimeno, M Concepción; Johnson, Alice; Marzo, Isabel

    2018-05-22

    The reactivity of the phosphonium salt, (cyanomethyl)triphenylphosphonium chloride, and the ylide, triphenylphosphoniumcyanomethylide, towards group eleven metal complexes is described. Mononuclear neutral gold(I) and gold(III) complexes of the type [AuX{CH(CN)PPh3}] or [AuX3{CH(CN)PPh3}], and cationic derivatives such as [AuL{CH(CN)PPh3}]X have been prepared. Surprisingly the cationic gold species could only be prepared with ligands with a large steric hindrance such as bulky NHCs or the JohnPhos phosphine, in contrast with silver and copper derivatives which have dimeric structures with coordination to the cyano group of the ylide. Bis(ylide)metal complexes have been synthesised in which a different structure is observed for gold compared to copper and silver. While gold shows mononuclear species, the silver complex presents a bidimensional polymeric structure as a result of further coordination of the silver centre to the nitrogen of the cyano group. These complexes possess two chiral centres and the gold compound is obtained as a mixture of diastereoisomers, whereas the copper and silver derivatives afford only one diastereroisomer. These compounds were screened for the in vitro cytotoxic activity against the human lung carcinoma cell line (A549). The IC50 values reveal an excellent cytotoxic activity for these metal complexes compared with cisplatin. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Research on the Micro Sheet Stamping Process Using Plasticine as Soft Punch

    PubMed Central

    Wang, Xiao; Zhang, Di; Gu, Chunxing; Shen, Zongbao; Liu, Huixia

    2014-01-01

    Plasticine is widely used in the analysis of metal forming processes, due to its excellent material flow ability. In this study, plasticine is used as the soft punch to fabricate array micro-channels on metal sheet in the micro sheet stamping process. This is because plasticine can produce a large material flow after being subjected to force and through the material flow, the plasticine can cause the sheet to fill into the micro-channels of the rigid die, leading to the generation of micro-channels in the sheet. The distribution of array micro-channels was investigated as well as the influence of load forces on the sheet deformations. It was found that the depth of micro-channels increases as the load force increases. When the load force reaches a certain level, a crack can be observed. The micro sheet stamping process was also investigated by the method of numerical simulation. The obtained experimental and numerical results for the stamping process showed that they were in good agreement. Additionally, from the simulation results, it can be seen that the corner region of the micro-channel-shape work piece has a risk to crack due to the existence of maximum von Mises stress and significant thinning. PMID:28788668

  5. Application of Δ- and λ-isomerism of octahedral metal complexes for inducing chiral nematic phases.

    PubMed

    Sato, Hisako; Yamagishi, Akihiko

    2009-11-20

    The Delta- and Lambda-isomerism of octahedral metal complexes is employed as a source of chirality for inducing chiral nematic phases. By applying a wide range of chiral metal complexes as a dopant, it has been found that tris(beta-diketonato)metal(III) complexes exhibit an extremely high value of helical twisting power. The mechanism of induction of the chiral nematic phase is postulated on the basis of a surface chirality model. The strategy for designing an efficient dopant is described, together with the results using a number of examples of Co(III), Cr(III) and Ru(III) complexes with C(2) symmetry. The development of photo-responsive dopants to achieve the photo-induced structural change of liquid crystal by use of photo-isomerization of chiral metal complexes is also described.

  6. Application of Δ- and Λ-Isomerism of Octahedral Metal Complexes for Inducing Chiral Nematic Phases

    PubMed Central

    Sato, Hisako; Yamagishi, Akihiko

    2009-01-01

    The Δ- and Λ-isomerism of octahedral metal complexes is employed as a source of chirality for inducing chiral nematic phases. By applying a wide range of chiral metal complexes as a dopant, it has been found that tris(β-diketonato)metal(III) complexes exhibit an extremely high value of helical twisting power. The mechanism of induction of the chiral nematic phase is postulated on the basis of a surface chirality model. The strategy for designing an efficient dopant is described, together with the results using a number of examples of Co(III), Cr(III) and Ru(III) complexes with C2 symmetry. The development of photo-responsive dopants to achieve the photo-induced structural change of liquid crystal by use of photo-isomerization of chiral metal complexes is also described. PMID:20057959

  7. Thermal and Mechanical Buckling Analysis of Hypersonic Aircraft Hat-Stiffened Panels With Varying Face Sheet Geometry and Fiber Orientation

    NASA Technical Reports Server (NTRS)

    Ko, William L.

    1996-01-01

    Mechanical and thermal buckling behavior of monolithic and metal-matrix composite hat-stiffened panels were investigated. The panels have three types of face-sheet geometry: Flat face sheet, microdented face sheet, and microbulged face sheet. The metal-matrix composite panels have three types of face-sheet layups, each of which is combined with various types of hat composite layups. Finite-element method was used in the eigenvalue extractions for both mechanical and thermal buckling. The thermal buckling analysis required both eigenvalue and material property iterations. Graphical methods of the dual iterations are shown. The mechanical and thermal buckling strengths of the hat-stiffened panels with different face-sheet geometry are compared. It was found that by just microdenting or microbulging of the face sheet, the axial, shear, and thermal buckling strengths of both types of hat-stiffened panels could be enhanced considerably. This effect is more conspicuous for the monolithic panels. For the metal-matrix composite panels, the effect of fiber orientations on the panel buckling strengths was investigated in great detail, and various composite layup combinations offering, high panel buckling strengths are presented. The axial buckling strength of the metal-matrix panel was sensitive to the change of hat fiber orientation. However, the lateral, shear, and thermal buckling strengths were insensitive to the change of hat fiber orientation.

  8. Properties of hot-rolled sheets from ferritic steel with increased strength

    NASA Astrophysics Data System (ADS)

    Perlovich, Yu.; Isaenkova, M.; Dobrokhotov, P.; Stolbov, S.; Bannykh, O.; Bannykh, I.; Antsyferova, M.

    2017-10-01

    Sheets from ferritic steel 3 mm thick with increased strength after thermal hardening were studied by use of various X-ray methods and mechanical testing. Rolling of steel was carried out at 1100°C with rather great reductions per pass, so that plastic deformation of metal spread by the significant distance from the surface. The texture of sheet proved to have two sharply different layers: the inner layer of ˜40% thick with the usual rolling texture of BCC metals and the external layer with the rolling texture of FCC metals. At that, within the intermediate layer the texture is weakened. Texture formation within the external layer is conditioned by the process of dynamical deformation ageing: interstitial impurities from atmosphere block dislocations, prevent from their slip and at increased temperatures promote their collective climb. As a result, the direction of lattice rotation as well as the final rolling texture change. Due to texture layering, by impact testing of the sheet the plane of crack propagation must be changed when this crack reaches the inner layer, and then an additional energy for its further movement is required. Thermal hardening of the sheet retains the type of rolling texture, though results in some its scattering, but at the same time the breaking point of steel grows twice owing to formation of intermetallic particles.

  9. Preparation and properties of chitosan-metal complex: Some factors influencing the adsorption capacity for dyes in aqueous solution.

    PubMed

    Rashid, Sadia; Shen, Chensi; Yang, Jing; Liu, Jianshe; Li, Jing

    2018-04-01

    Chitosan-metal complexes have been widely studied in wastewater treatment, but there are still various factors in complex preparation which are collectively responsible for improving the adsorption capacity need to be further studied. Thus, this study investigates the factors affecting the adsorption ability of chitosan-metal complex adsorbents, including various kinds of metal centers, different metal salts and crosslinking degree. The results show that the chitosan-Fe(III) complex prepared by sulfate salts exhibited the best adsorption efficiency (100%) for various dyes in very short time duration (10min), and its maximum adsorption capacity achieved 349.22mg/g. The anion of the metal salt which was used in preparation played an important role to enhance the adsorption ability of chitosan-metal complex. SO 4 2- ions not only had the effect of crosslinking through electrostatic interaction with amine group of chitosan polymer, but also could facilitate the chelation of metal ions with chitosan polymer during the synthesis process. Additionally, the pH sensitivity and the sensitivity of ionic environment for chitosan-metal complex were analyzed. We hope that these factors affecting the adsorption of the chitosan-metal complex can help not only in optimizing its use but also in designing new chitosan-metal based complexes. Copyright © 2017. Published by Elsevier B.V.

  10. Optimization of CO2 laser cutting parameters on Austenitic type Stainless steel sheet

    NASA Astrophysics Data System (ADS)

    Parthiban, A.; Sathish, S.; Chandrasekaran, M.; Ravikumar, R.

    2017-03-01

    Thin AISI 316L stainless steel sheet widely used in sheet metal processing industries for specific applications. CO2 laser cutting is one of the most popular sheet metal cutting processes for cutting of sheets in different profile. In present work various cutting parameters such as laser power (2000 watts-4000 watts), cutting speed (3500mm/min - 5500 mm/min) and assist gas pressure (0.7 Mpa-0.9Mpa) for cutting of AISI 316L 2mm thickness stainless sheet. This experimentation was conducted based on Box-Behenken design. The aim of this work is to develop a mathematical model kerf width for straight and curved profile through response surface methodology. The developed mathematical models for straight and curved profile have been compared. The Quadratic models have the best agreement with experimental data, and also the shape of the profile a substantial role in achieving to minimize the kerf width. Finally the numerical optimization technique has been used to find out best optimum laser cutting parameter for both straight and curved profile cut.

  11. Use of acrylic sheet molds for elastomeric products

    NASA Technical Reports Server (NTRS)

    Heisman, R. M.; Koerner, A. E.; Messineo, S. M.

    1970-01-01

    Molds constructed of acrylic sheet are more easily machined than metal, are transparent to ensure complete filling during injection, and have smooth surfaces free of contamination. Technique eliminates flashing on molded parts and mold release agents.

  12. An ice sheet model validation framework for the Greenland ice sheet

    NASA Astrophysics Data System (ADS)

    Price, Stephen F.; Hoffman, Matthew J.; Bonin, Jennifer A.; Howat, Ian M.; Neumann, Thomas; Saba, Jack; Tezaur, Irina; Guerber, Jeffrey; Chambers, Don P.; Evans, Katherine J.; Kennedy, Joseph H.; Lenaerts, Jan; Lipscomb, William H.; Perego, Mauro; Salinger, Andrew G.; Tuminaro, Raymond S.; van den Broeke, Michiel R.; Nowicki, Sophie M. J.

    2017-01-01

    We propose a new ice sheet model validation framework - the Cryospheric Model Comparison Tool (CmCt) - that takes advantage of ice sheet altimetry and gravimetry observations collected over the past several decades and is applied here to modeling of the Greenland ice sheet. We use realistic simulations performed with the Community Ice Sheet Model (CISM) along with two idealized, non-dynamic models to demonstrate the framework and its use. Dynamic simulations with CISM are forced from 1991 to 2013, using combinations of reanalysis-based surface mass balance and observations of outlet glacier flux change. We propose and demonstrate qualitative and quantitative metrics for use in evaluating the different model simulations against the observations. We find that the altimetry observations used here are largely ambiguous in terms of their ability to distinguish one simulation from another. Based on basin-scale and whole-ice-sheet-scale metrics, we find that simulations using both idealized conceptual models and dynamic, numerical models provide an equally reasonable representation of the ice sheet surface (mean elevation differences of < 1 m). This is likely due to their short period of record, biases inherent to digital elevation models used for model initial conditions, and biases resulting from firn dynamics, which are not explicitly accounted for in the models or observations. On the other hand, we find that the gravimetry observations used here are able to unambiguously distinguish between simulations of varying complexity, and along with the CmCt, can provide a quantitative score for assessing a particular model and/or simulation. The new framework demonstrates that our proposed metrics can distinguish relatively better from relatively worse simulations and that dynamic ice sheet models, when appropriately initialized and forced with the right boundary conditions, demonstrate a predictive skill with respect to observed dynamic changes that have occurred on

  13. An ice sheet model validation framework for the Greenland ice sheet

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Price, Stephen F.; Hoffman, Matthew J.; Bonin, Jennifer A.

    We propose a new ice sheet model validation framework the Cryospheric Model Comparison Tool (CMCT) that takes advantage of ice sheet altimetry and gravimetry observations collected over the past several decades and is applied here to modeling of the Greenland ice sheet. We use realistic simulations performed with the Community Ice Sheet Model (CISM) along with two idealized, non-dynamic models to demonstrate the framework and its use. Dynamic simulations with CISM are forced from 1991 to 2013 using combinations of reanalysis-based surface mass balance and observations of outlet glacier flux change. We propose and demonstrate qualitative and quanti- tative metricsmore » for use in evaluating the different model simulations against the observations. We find 10 that the altimetry observations used here are largely ambiguous in terms of their ability to distinguish one simulation from another. Based on basin- and whole-ice-sheet scale metrics, the model initial condition as well as output from idealized and dynamic models all provide an equally reasonable representation of the ice sheet surface (mean elevation differences of <1 m). This is likely due to their short period of record, biases inherent to digital elevation models used for model initial conditions, and biases resulting from firn dynamics, which are not explicitly accounted for in the models or observations. On the other hand, we find that the gravimetry observations used here are able to unambiguously distinguish between simulations of varying complexity, and along with the CMCT, can provide a quantitative score for assessing a particular model and/or simulation. The new framework demonstrates that our proposed metrics can distinguish relatively better from relatively worse simulations and that dynamic ice sheet models, when appropriately initialized and forced with the right boundary conditions, demonstrate predictive skill with respect to observed dynamic changes occurring on Greenland over the past few

  14. An ice sheet model validation framework for the Greenland ice sheet

    PubMed Central

    Price, Stephen F.; Hoffman, Matthew J.; Bonin, Jennifer A.; Howat, Ian M.; Neumann, Thomas; Saba, Jack; Tezaur, Irina; Guerber, Jeffrey; Chambers, Don P.; Evans, Katherine J.; Kennedy, Joseph H.; Lenaerts, Jan; Lipscomb, William H.; Perego, Mauro; Salinger, Andrew G.; Tuminaro, Raymond S.; van den Broeke, Michiel R.; Nowicki, Sophie M. J.

    2018-01-01

    We propose a new ice sheet model validation framework – the Cryospheric Model Comparison Tool (CmCt) – that takes advantage of ice sheet altimetry and gravimetry observations collected over the past several decades and is applied here to modeling of the Greenland ice sheet. We use realistic simulations performed with the Community Ice Sheet Model (CISM) along with two idealized, non-dynamic models to demonstrate the framework and its use. Dynamic simulations with CISM are forced from 1991 to 2013 using combinations of reanalysis-based surface mass balance and observations of outlet glacier flux change. We propose and demonstrate qualitative and quantitative metrics for use in evaluating the different model simulations against the observations. We find that the altimetry observations used here are largely ambiguous in terms of their ability to distinguish one simulation from another. Based on basin- and whole-ice-sheet scale metrics, we find that simulations using both idealized conceptual models and dynamic, numerical models provide an equally reasonable representation of the ice sheet surface (mean elevation differences of <1 m). This is likely due to their short period of record, biases inherent to digital elevation models used for model initial conditions, and biases resulting from firn dynamics, which are not explicitly accounted for in the models or observations. On the other hand, we find that the gravimetry observations used here are able to unambiguously distinguish between simulations of varying complexity, and along with the CmCt, can provide a quantitative score for assessing a particular model and/or simulation. The new framework demonstrates that our proposed metrics can distinguish relatively better from relatively worse simulations and that dynamic ice sheet models, when appropriately initialized and forced with the right boundary conditions, demonstrate predictive skill with respect to observed dynamic changes occurring on Greenland over the

  15. An ice sheet model validation framework for the Greenland ice sheet.

    PubMed

    Price, Stephen F; Hoffman, Matthew J; Bonin, Jennifer A; Howat, Ian M; Neumann, Thomas; Saba, Jack; Tezaur, Irina; Guerber, Jeffrey; Chambers, Don P; Evans, Katherine J; Kennedy, Joseph H; Lenaerts, Jan; Lipscomb, William H; Perego, Mauro; Salinger, Andrew G; Tuminaro, Raymond S; van den Broeke, Michiel R; Nowicki, Sophie M J

    2017-01-01

    We propose a new ice sheet model validation framework - the Cryospheric Model Comparison Tool (CmCt) - that takes advantage of ice sheet altimetry and gravimetry observations collected over the past several decades and is applied here to modeling of the Greenland ice sheet. We use realistic simulations performed with the Community Ice Sheet Model (CISM) along with two idealized, non-dynamic models to demonstrate the framework and its use. Dynamic simulations with CISM are forced from 1991 to 2013 using combinations of reanalysis-based surface mass balance and observations of outlet glacier flux change. We propose and demonstrate qualitative and quantitative metrics for use in evaluating the different model simulations against the observations. We find that the altimetry observations used here are largely ambiguous in terms of their ability to distinguish one simulation from another. Based on basin- and whole-ice-sheet scale metrics, we find that simulations using both idealized conceptual models and dynamic, numerical models provide an equally reasonable representation of the ice sheet surface (mean elevation differences of <1 m). This is likely due to their short period of record, biases inherent to digital elevation models used for model initial conditions, and biases resulting from firn dynamics, which are not explicitly accounted for in the models or observations. On the other hand, we find that the gravimetry observations used here are able to unambiguously distinguish between simulations of varying complexity, and along with the CmCt, can provide a quantitative score for assessing a particular model and/or simulation. The new framework demonstrates that our proposed metrics can distinguish relatively better from relatively worse simulations and that dynamic ice sheet models, when appropriately initialized and forced with the right boundary conditions, demonstrate predictive skill with respect to observed dynamic changes occurring on Greenland over the past

  16. An ice sheet model validation framework for the Greenland ice sheet

    DOE PAGES

    Price, Stephen F.; Hoffman, Matthew J.; Bonin, Jennifer A.; ...

    2017-01-17

    We propose a new ice sheet model validation framework the Cryospheric Model Comparison Tool (CMCT) that takes advantage of ice sheet altimetry and gravimetry observations collected over the past several decades and is applied here to modeling of the Greenland ice sheet. We use realistic simulations performed with the Community Ice Sheet Model (CISM) along with two idealized, non-dynamic models to demonstrate the framework and its use. Dynamic simulations with CISM are forced from 1991 to 2013 using combinations of reanalysis-based surface mass balance and observations of outlet glacier flux change. We propose and demonstrate qualitative and quanti- tative metricsmore » for use in evaluating the different model simulations against the observations. We find 10 that the altimetry observations used here are largely ambiguous in terms of their ability to distinguish one simulation from another. Based on basin- and whole-ice-sheet scale metrics, the model initial condition as well as output from idealized and dynamic models all provide an equally reasonable representation of the ice sheet surface (mean elevation differences of <1 m). This is likely due to their short period of record, biases inherent to digital elevation models used for model initial conditions, and biases resulting from firn dynamics, which are not explicitly accounted for in the models or observations. On the other hand, we find that the gravimetry observations used here are able to unambiguously distinguish between simulations of varying complexity, and along with the CMCT, can provide a quantitative score for assessing a particular model and/or simulation. The new framework demonstrates that our proposed metrics can distinguish relatively better from relatively worse simulations and that dynamic ice sheet models, when appropriately initialized and forced with the right boundary conditions, demonstrate predictive skill with respect to observed dynamic changes occurring on Greenland over the past few

  17. An Ice Sheet Model Validation Framework for the Greenland Ice Sheet

    NASA Technical Reports Server (NTRS)

    Price, Stephen F.; Hoffman, Matthew J.; Bonin, Jennifer A.; Howat, Ian M.; Neumann, Thomas A.; Saba, Jack; Tezaur, Irina; Guerber, Jeffrey R.; Chambers, Don P.; Evans, Katherine J.; hide

    2017-01-01

    We propose a new ice sheet model validation framework - the Cryospheric Model Comparison Tool (CmCt) - that takes advantage of ice sheet altimetry and gravimetry observations collected over the past several decades and is applied here to modeling of the Greenland ice sheet. We use realistic simulations performed with the Community Ice Sheet Model (CISM) along with two idealized, non-dynamic models to demonstrate the framework and its use. Dynamic simulations with CISM are forced from 1991 to 2013, using combinations of reanalysis-based surface mass balance and observations of outlet glacier flux change. We propose and demonstrate qualitative and quantitative metrics for use in evaluating the different model simulations against the observations. We find that the altimetry observations used here are largely ambiguous in terms of their ability to distinguish one simulation from another. Based on basin-scale and whole-ice-sheet-scale metrics, we find that simulations using both idealized conceptual models and dynamic, numerical models provide an equally reasonable representation of the ice sheet surface (mean elevation differences of less than 1 meter). This is likely due to their short period of record, biases inherent to digital elevation models used for model initial conditions, and biases resulting from firn dynamics, which are not explicitly accounted for in the models or observations. On the other hand, we find that the gravimetry observations used here are able to unambiguously distinguish between simulations of varying complexity, and along with the CmCt, can provide a quantitative score for assessing a particular model and/or simulation. The new framework demonstrates that our proposed metrics can distinguish relatively better from relatively worse simulations and that dynamic ice sheet models, when appropriately initialized and forced with the right boundary conditions, demonstrate a predictive skill with respect to observed dynamic changes that have occurred

  18. Emittance Measurements for a Thin Liquid Sheet Flow

    NASA Technical Reports Server (NTRS)

    Englehart, Amy N.; McConley, Marc W.; Chubb, Donald L.

    1996-01-01

    The Liquid Sheet Radiator (LSR) is an external flow radiator that uses a triangular-shaped flowing liquid sheet as the radiating surface. It has potentially much lower mass than solid wall radiators such as pumped loop and heat pipe radiators, along with being nearly immune to micrometeoroid penetration. The LSR has an added advantage of simplicity. Surface tension causes a thin (100-300 microns) liquid sheet to coalesce to a point, causing the sheet flow to have a triangular shape. Such a triangular sheet is desirable since it allows for simple collection of the flow at a single point. A major problem for all external flow radiators is the requirement that the working fluid be of very low (approx. 10(sup -8) torr) vapor pressure to keep evaporative losses low. As a result, working fluids are limited to certain oils (such as used in diffusion pumps) for low temperatures (300-400 K) and liquid metals for higher temperatures. Previous research on the LSR has been directed at understanding the fluid mechanics of thin sheet flows and assessing the stability of such flows, especially with regard to the formation of holes in the sheet. Taylor studied extensively the stability of thin liquid sheets both theoretically and experimentally. He showed that thin sheets in a vacuum are stable. The latest research has been directed at determining the emittance of thin sheet flows. The emittance was calculated from spectral transmittance data for the Dow Corning 705 silicone oil. By experimentally setting up a sheet flow, the emittance was also determined as a function of measurable quantities, most importantly, the temperature drop between the top of the sheet and the temperature at the coalescence point of the sheet. Temperature fluctuations upstream of the liquid sheet were a potential problem in the analysis and were investigated.

  19. Polymer quenched prealloyed metal powder

    DOEpatents

    Hajaligol, Mohammad R.; Fleischhauer, Grier; German, Randall M.

    2001-01-01

    A powder metallurgical process of preparing a sheet from a powder having an intermetallic alloy composition such as an iron, nickel or titanium aluminide. The sheet can be manufactured into electrical resistance heating elements having improved room temperature ductility, electrical resistivity, cyclic fatigue resistance, high temperature oxidation resistance, low and high temperature strength, and/or resistance to high temperature sagging. The iron aluminide has an entirely ferritic microstructure which is free of austenite and can include, in weight %, 4 to 32% Al, and optional additions such as .ltoreq.1% Cr, .gtoreq.0.05% Zr .ltoreq.2% Ti, .ltoreq.2% Mo, .ltoreq.1% Ni, .ltoreq.0.75% C, .ltoreq.0.1% B, .ltoreq.1% submicron oxide particles and/or electrically insulating or electrically conductive covalent ceramic particles, .ltoreq.1% rare earth metal, and/or .ltoreq.3 % Cu. The process includes forming a non-densified metal sheet by consolidating a powder having an intermetallic alloy composition such as by roll compaction, tape casting or plasma spraying, forming a cold rolled sheet by cold rolling the non-densified metal sheet so as to increase the density and reduce the thickness thereof and annealing the cold rolled sheet. The powder can be a water, polymer or gas atomized powder which is subjecting to sieving and/or blending with a binder prior to the consolidation step. After the consolidation step, the sheet can be partially sintered. The cold rolling and/or annealing steps can be repeated to achieve the desired sheet thickness and properties. The annealing can be carried out in a vacuum furnace with a vacuum or inert atmosphere. During final annealing, the cold rolled sheet recrystallizes to an average grain size of about 10 to 30 .mu.m. Final stress relief annealing can be carried out in the B2 phase temperature range.

  20. Synthesis and spectral studies of platinum metal complexes of benzoin thiosemicarbazone

    NASA Astrophysics Data System (ADS)

    Offiong, Offiong E.

    1994-11-01

    The platinum metal chelates of benzoin thiosemicarbazone obtained with Ru(III), Rh(III), Ir(III), Pd(II) and Pt(II) were prepared from their corresponding halide salts. The complexes were characterized by elemental analysis, conductance measurement, IR, Raman, 1H-NMR, 13C-NMR and UV-visible spectra studies. Various ligand field parameters and nephelauxetic parameters were also calculated. The mode of bonding and the geometry of the ligand environment around the metal ion have been discussed in the light of the available data obtained. Complexes of Ru(III), Rh(III) and Ir(III) are six-coordinate octahedral, while Pd(II) and Pt(II) halide complexes are four-coordinated with halides bridging.

  1. Dinuclear PhotoCORMs: Dioxygen-Assisted Carbon Monoxide Uncaging from Long-Wavelength-Absorbing Metal-Metal-Bonded Carbonyl Complexes.

    PubMed

    Li, Zhi; Pierri, Agustin E; Huang, Po-Ju; Wu, Guang; Iretskii, Alexei V; Ford, Peter C

    2017-06-05

    We describe a new strategy for triggering the photochemical release of caged carbon monoxide (CO) in aerobic media using long-wavelength visible and near-infrared (NIR) light. The dinuclear rhenium-manganese carbonyl complexes (CO) 5 ReMn(CO) 3 (L), where L = phenanthroline (1), bipyridine (2), biquinoline (3), or phenanthrolinecarboxaldehyde (4), each show a strong metal-metal-bond-to-ligand (σ MM → π L *) charge-transfer absorption band at longer wavelengths. Photolysis with deep-red (1 and 2) or NIR (3 and 4) light leads to homolytic cleavage of the Re-Mn bonds to give mononuclear metal radicals. In the absence of trapping agents, these radicals primarily recombine to reform dinuclear complexes. In oxygenated media, however, the radicals react with dioxygen to form species much more labile toward CO release via secondary thermal and/or photochemical reactions. Conjugation of 4, with an amine-terminated poly(ethylene glycol) oligomer, gives a water-soluble derivative with similar photochemistry. In this context, we discuss the potential applications of these dinuclear complexes as visible/NIR-light-photoactivated CO-releasing moieties (photoCORMs).

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

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

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

  3. Ultra-broadband microwave metamaterial absorber based on resistive sheets

    NASA Astrophysics Data System (ADS)

    Kim, Y. J.; Yoo, Y. J.; Hwang, J. S.; Lee, Y. P.

    2017-01-01

    We investigate a broadband perfect absorber for microwave frequencies, with a wide incident angle, using resistive sheets, based on both simulation and experiment. The absorber uses periodically-arranged meta-atoms, consisting of snake-shape metallic patterns and metal planes separated by three resistive sheet layers between four dielectric layers. We demonstrate the mechanism of the broadband by impedance matching with free space, and the distribution of surface currents at specific frequencies. In simulation, the absorption was over 96% in 1.4-6.0 GHz. The corresponding experimental absorption band over 96% was 1.4-4.0 GHz, however, the absorption was lower than 96% in the 4.0-6.0 GHz range because of the rather irregular thickness of the resistive sheets. Furthermore, it works for wide incident angles and is relatively independent of polarization. The design is scalable to smaller sizes in the THz range. The results of this study show potential for real applications in prevention of microwave frequency exposure, with devices such as cell phones, monitors, and microwave equipment.

  4. 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.

  5. 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.

  6. Shape and symmetry of heptacoordinate transition-metal complexes: structural trends.

    PubMed

    Casanova, David; Alemany, Pere; Bofill, Josep M; Alvarez, Santiago

    2003-03-17

    The stereochemistries of heptacoordinate transition-metal complexes are analyzed by using continuous symmetry and shape measures of their coordination spheres. The distribution of heptacoordination through the transition-metal series is presented based on structural database searches including organometallic and Werner-type molecular complexes, metalloproteins, and extended solids. The most common polyhedron seems to be the pentagonal bipyramid, while different preferences are found for specific families of compounds, as in the complexes with three or four carbonyl or phosphine ligands, which prefer the capped octahedron or the capped trigonal prism rather than the pentagonal bipyramid. The symmetry maps for heptacoordination are presented and shown to be helpful for detecting stereochemical trends. The maximal symmetry interconversion pathways between the three most common polyhedra are defined in terms of symmetry constants and a large number of experimental structures are seen to fall along those paths.

  7. Seismic evidence for complex sedimentary control of Greenland Ice Sheet flow

    PubMed Central

    Kulessa, Bernd; Hubbard, Alun L.; Booth, Adam D.; Bougamont, Marion; Dow, Christine F.; Doyle, Samuel H.; Christoffersen, Poul; Lindbäck, Katrin; Pettersson, Rickard; Fitzpatrick, Andrew A. W.; Jones, Glenn A.

    2017-01-01

    The land-terminating margin of the Greenland Ice Sheet has slowed down in recent decades, although the causes and implications for future ice flow are unclear. Explained originally by a self-regulating mechanism where basal slip reduces as drainage evolves from low to high efficiency, recent numerical modeling invokes a sedimentary control of ice sheet flow as an alternative hypothesis. Although both hypotheses can explain the recent slowdown, their respective forecasts of a long-term deceleration versus an acceleration of ice flow are contradictory. We present amplitude-versus-angle seismic data as the first observational test of the alternative hypothesis. We document transient modifications of basal sediment strengths by rapid subglacial drainages of supraglacial lakes, the primary current control on summer ice sheet flow according to our numerical model. Our observations agree with simulations of initial postdrainage sediment weakening and ice flow accelerations, and subsequent sediment restrengthening and ice flow decelerations, and thus confirm the alternative hypothesis. Although simulated melt season acceleration of ice flow due to weakening of subglacial sediments does not currently outweigh winter slowdown forced by self-regulation, they could dominate over the longer term. Subglacial sediments beneath the Greenland Ice Sheet must therefore be mapped and characterized, and a sedimentary control of ice flow must be evaluated against competing self-regulation mechanisms. PMID:28835915

  8. Seismic evidence for complex sedimentary control of Greenland Ice Sheet flow.

    PubMed

    Kulessa, Bernd; Hubbard, Alun L; Booth, Adam D; Bougamont, Marion; Dow, Christine F; Doyle, Samuel H; Christoffersen, Poul; Lindbäck, Katrin; Pettersson, Rickard; Fitzpatrick, Andrew A W; Jones, Glenn A

    2017-08-01

    The land-terminating margin of the Greenland Ice Sheet has slowed down in recent decades, although the causes and implications for future ice flow are unclear. Explained originally by a self-regulating mechanism where basal slip reduces as drainage evolves from low to high efficiency, recent numerical modeling invokes a sedimentary control of ice sheet flow as an alternative hypothesis. Although both hypotheses can explain the recent slowdown, their respective forecasts of a long-term deceleration versus an acceleration of ice flow are contradictory. We present amplitude-versus-angle seismic data as the first observational test of the alternative hypothesis. We document transient modifications of basal sediment strengths by rapid subglacial drainages of supraglacial lakes, the primary current control on summer ice sheet flow according to our numerical model. Our observations agree with simulations of initial postdrainage sediment weakening and ice flow accelerations, and subsequent sediment restrengthening and ice flow decelerations, and thus confirm the alternative hypothesis. Although simulated melt season acceleration of ice flow due to weakening of subglacial sediments does not currently outweigh winter slowdown forced by self-regulation, they could dominate over the longer term. Subglacial sediments beneath the Greenland Ice Sheet must therefore be mapped and characterized, and a sedimentary control of ice flow must be evaluated against competing self-regulation mechanisms.

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

    PubMed

    Lindahl, Paul A; Moore, Michael J

    2016-08-02

    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

  10. Metal nanoparticle-graphene oxide composites: Photophysical properties and sensing applications

    NASA Astrophysics Data System (ADS)

    Murphy, Sean J.

    Composite nanomaterials allow for attractive properties of multiple functional components to be combined. Fundamental understanding of the interaction between different nanomaterials, their surroundings, and nearby molecular species is pertinent for implementation into devices. Metal nanoparticles have been used for their optical properties in many applications including stained glass, cancer therapy, solar steam generation, surface enhanced Raman spectroscopy (SERS), and catalysis. Carbon-based nanomaterials such as graphene and carbon nanotubes show potential for a wide variety of applications including solar energy harvesting, chemical sensors, and electronics. Combining useful and in some cases new properties of composite nanomaterials offers exciting opportunities in fundamental science and device development. In this dissertation, I aim to address understanding photoinduced interaction between porphyrin and silver nanoparticles, inter-sheet interaction between stacked graphene oxide (GO) sheets in thin films, complexation of reduced GO with Raman active target molecule in SERS applications, and efficacy of graphene-metal nanoparticle composites for sensing applications. Molecule-metal nanoparticle composite material made up of photoactive porphyrin and silver nanoparticles was studied using various spectroscopic tools. UV-visible absorption and surface enhanced Raman spectroscopic results suggest formation of a charge-transfer complex for porphyrin-silver nanoparticle composite. Ultrafast transient absorption and fluorescence upconversion spectroscopies further corroborate electronic interaction by providing evidence for excited state electron transfer between porphyrin and silver nanoparticles. Understanding electronic interaction between adsorbed photoactive molecules and metal nanoparticles may be of use for applications in photocatalysis or light-energy harvesting. Graphene oxide (GO) thin films have been prepared and studied using transient absorption

  11. 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.

  12. 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)

  13. 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…

  14. Thin sheets achieve optimal wrapping of liquids

    NASA Astrophysics Data System (ADS)

    Paulsen, Joseph; Démery, Vincent; Davidovitch, Benny; Santangelo, Christian; Russell, Thomas; Menon, Narayanan

    2015-03-01

    A liquid drop can wrap itself in a sheet using capillary forces [Py et al., PRL 98, 2007]. However, the efficiency of ``capillary origami'' at covering the surface of a drop is hampered by the mechanical cost of bending the sheet. Thinner sheets deform more readily by forming small-scale wrinkles and stress-focussing patterns, but it is unclear how coverage efficiency competes with mechanical cost as thickness is decreased, and what wrapping shapes will emerge. We place a thin (~ 100 nm) polymer film on a drop whose volume is gradually decreased so that the sheet covers an increasing fraction of its surface. The sheet exhibits a complex sequence of axisymmetric and polygonal partially- and fully- wrapped shapes. Remarkably, the progression appears independent of mechanical properties. The gross shape, which neglects small-scale features, is correctly predicted by a simple geometric approach wherein the exposed area is minimized. Thus, simply using a thin enough sheet results in maximal coverage.

  15. A low-spin Fe(III) complex with 100-ps ligand-to-metal charge transfer photoluminescence

    NASA Astrophysics Data System (ADS)

    Chábera, Pavel; Liu, Yizhu; Prakash, Om; Thyrhaug, Erling; Nahhas, Amal El; Honarfar, Alireza; Essén, Sofia; Fredin, Lisa A.; Harlang, Tobias C. B.; Kjær, Kasper S.; Handrup, Karsten; Ericson, Fredric; Tatsuno, Hideyuki; Morgan, Kelsey; Schnadt, Joachim; Häggström, Lennart; Ericsson, Tore; Sobkowiak, Adam; Lidin, Sven; Huang, Ping; Styring, Stenbjörn; Uhlig, Jens; Bendix, Jesper; Lomoth, Reiner; Sundström, Villy; Persson, Petter; Wärnmark, Kenneth

    2017-03-01

    Transition-metal complexes are used as photosensitizers, in light-emitting diodes, for biosensing and in photocatalysis. A key feature in these applications is excitation from the ground state to a charge-transfer state; the long charge-transfer-state lifetimes typical for complexes of ruthenium and other precious metals are often essential to ensure high performance. There is much interest in replacing these scarce elements with Earth-abundant metals, with iron and copper being particularly attractive owing to their low cost and non-toxicity. But despite the exploration of innovative molecular designs, it remains a formidable scientific challenge to access Earth-abundant transition-metal complexes with long-lived charge-transfer excited states. No known iron complexes are considered photoluminescent at room temperature, and their rapid excited-state deactivation precludes their use as photosensitizers. Here we present the iron complex [Fe(btz)3]3+ (where btz is 3,3‧-dimethyl-1,1‧-bis(p-tolyl)-4,4‧-bis(1,2,3-triazol-5-ylidene)), and show that the superior σ-donor and π-acceptor electron properties of the ligand stabilize the excited state sufficiently to realize a long charge-transfer lifetime of 100 picoseconds (ps) and room-temperature photoluminescence. This species is a low-spin Fe(III) d5 complex, and emission occurs from a long-lived doublet ligand-to-metal charge-transfer (2LMCT) state that is rarely seen for transition-metal complexes. The absence of intersystem crossing, which often gives rise to large excited-state energy losses in transition-metal complexes, enables the observation of spin-allowed emission directly to the ground state and could be exploited as an increased driving force in photochemical reactions on surfaces. These findings suggest that appropriate design strategies can deliver new iron-based materials for use as light emitters and photosensitizers.

  16. Understanding M-ligand bonding and mer-/fac-isomerism in tris(8-hydroxyquinolinate) metallic complexes.

    PubMed

    Lima, Carlos F R A C; Taveira, Ricardo J S; Costa, José C S; Fernandes, Ana M; Melo, André; Silva, Artur M S; Santos, Luís M N B F

    2016-06-28

    Tris(8-hydroxyquinolinate) metallic complexes, Mq3, are one of the most important classes of organic semiconductor materials. Herein, the nature of the chemical bond in Mq3 complexes and its implications on their molecular properties were investigated by a combined experimental and computational approach. Various Mq3 complexes, resulting from the alteration of the metal and substitution of the 8-hydroxyquinoline ligand in different positions, were prepared. The mer-/fac-isomerism in Mq3 was explored by FTIR and NMR spectroscopy, evidencing that, irrespective of the substituent, mer- and fac-are the most stable molecular configurations of Al(iii) and In(iii) complexes, respectively. The relative M-ligand bond dissociation energies were evaluated experimentally by electrospray ionization tandem mass spectrometry (ESI-MS-MS), showing a non-monotonous variation along the group (Al > In > Ga). The results reveal a strong covalent character in M-ligand bonding, which allows for through-ligand electron delocalization, and explain the preferred molecular structures of Mq3 complexes as resulting from the interplay between bonding and steric factors. The mer-isomer reduces intraligand repulsions, being preferred for smaller metals, while the fac-isomer is favoured for larger metals where stronger covalent M-ligand bonds can be formed due to more extensive through-ligand conjugation mediated by metal "d" orbitals.

  17. Effects of lability of metal complex on free ion measurement using DMT.

    PubMed

    Weng, Liping; Van Riemsdijk, Willem H; Temminghoff, Erwin J M

    2010-04-01

    Very low concentrations of free metal ion in natural samples can be measured using the Donnan membrane technique (DMT) based on ion transport kinetics. In this paper, the possible effects of slow dissociation of metal complexes on the interpretation of kinetic DMT are investigated both theoretically and experimentally. The expressions of the lability parameter, Lgrangian , were derived for DMT. Analysis of new experimental studies using synthetic solution containing NTA as the ligand and Cu(2+) ions shows that when the ionic strength is low (complex metals. By comparing the fraction of labile species measured using other dynamic sensors (DGT, GIME) in several freshwaters, it is concluded that in most waters ion transport in DMT is controlled by diffusion in the membrane. Only in very soft waters (<0.7 mM Ca+Mg), the dissociation rate of natural metal complex may influence ion transport in DMT. In this case, neglecting this effect may lead to an underestimation of the free metal ion concentration measured.

  18. Processing experiments on non-Czochralski silicon sheet

    NASA Technical Reports Server (NTRS)

    Pryor, R. A.; Grenon, L. A.; Sakiotis, N. G.; Pastirik, E. M.; Sparks, T. O.; Legge, R. N.

    1981-01-01

    A program is described which supports and promotes the development of processing techniques which may be successfully and cost-effectively applied to low-cost sheets for solar cell fabrication. Results are reported in the areas of process technology, cell design, cell metallization, and production cost simulation.

  19. 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.

  20. Preparation, characterization and biological activity of novel metal-NNNN donor Schiff base complexes

    NASA Astrophysics Data System (ADS)

    Mohamed, Gehad G.; Omar, M. M.; Ibrahim, Amr A.

    2010-02-01

    Novel Schiff base (H 2L) ligand is prepared via condensation of benzil and triethylenetetraamine. The ligand is characterized based on elemental analysis, mass, IR and 1H NMR spectra. Metal complexes are reported and characterized based on elemental analyses, IR, 1H NMR, solid reflectance, magnetic moment, molar conductance, and thermal analyses (TG, DTG and DTA). 1:1 [M]:[H 2L] complexes are found from the elemental analyses data having the formulae [M(H 2L)Cl 2]· yH 2O (M = Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II)), [Fe(H 2L)Cl 2]Cl·H 2O, [Th(H 2L)Cl 2]Cl 2·3H 2O and [UO 2(H 2L)](CH 3COO) 2·2H 2O. The metal chelates are found to be non-electrolytes except Fe(III), Th(IV) and UO 2(II) complexes are electrolytes. IR spectra show that H 2L is coordinated to the metal ions in a neutral tetradentate manner with 4Ns donor sites of the two azomethine N and two NH groups. The geometrical structures of these complexes are found to be octahedral. The thermal behaviour of these chelates is studied where the hydrated complexes lose water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps. The activation thermodynamic parameters are calculated using Coats-Redfern method. The ligand (H 2L), in comparison to its metal complexes, is screened for its antibacterial activity. The activity data show that the metal complexes have antibacterial activity more than the parent Schiff base ligand and cefepime standard against one or more bacterial species.

  1. 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.

  2. Environmental and Body Concentrations of Heavy Metals at Sites Near and Distant from Industrial Complexes in Ulsan, Korea.

    PubMed

    Sung, Joo Hyun; Oh, Inbo; Kim, Ahra; Lee, Jiho; Sim, Chang Sun; Yoo, Cheolin; Park, Sang Jin; Kim, Geun Bae; Kim, Yangho

    2018-01-29

    Industrial pollution may affect the heavy metal body burden of people living near industrial complexes. We determined the average concentrations of atmospheric heavy metals in areas close to and distant from industrial complexes in Korea, and the body concentrations of these heavy metals in residents living near and distant from these facilities. The atmospheric data of heavy metals (lead and cadmium) were from the Regional Air Monitoring Network in Ulsan. We recruited 1,148 participants, 872 who lived near an industrial complex ("exposed" group) and 276 who lived distant from industrial complexes ("non-exposed" group), and measured their concentrations of blood lead, urinary cadmium, and urinary total mercury. The results showed that atmospheric and human concentrations of heavy metals were higher in areas near industrial complexes. In addition, residents living near industrial complexes had higher individual and combined concentrations (cadmium + lead + mercury) of heavy metals. We conclude that residents living near industrial complexes are exposed to high concentrations of heavy metals, and should be carefully monitored. © 2018 The Korean Academy of Medical Sciences.

  3. Environmental and Body Concentrations of Heavy Metals at Sites Near and Distant from Industrial Complexes in Ulsan, Korea

    PubMed Central

    2017-01-01

    Background Industrial pollution may affect the heavy metal body burden of people living near industrial complexes. We determined the average concentrations of atmospheric heavy metals in areas close to and distant from industrial complexes in Korea, and the body concentrations of these heavy metals in residents living near and distant from these facilities. Methods The atmospheric data of heavy metals (lead and cadmium) were from the Regional Air Monitoring Network in Ulsan. We recruited 1,148 participants, 872 who lived near an industrial complex (“exposed” group) and 276 who lived distant from industrial complexes (“non-exposed” group), and measured their concentrations of blood lead, urinary cadmium, and urinary total mercury. Results The results showed that atmospheric and human concentrations of heavy metals were higher in areas near industrial complexes. In addition, residents living near industrial complexes had higher individual and combined concentrations (cadmium + lead + mercury) of heavy metals. Conclusion We conclude that residents living near industrial complexes are exposed to high concentrations of heavy metals, and should be carefully monitored. PMID:29349943

  4. Spectroscopic investigation and luminescent properties of Schiff base metal complex for OLED

    NASA Astrophysics Data System (ADS)

    Gondia, N. K.; Priya, J.; Sharma, S. K.

    2018-05-01

    Organic light emitting diode (OLED) display technology has demonstrated high efficiency and brightness, is leading to a strong commercial interest. One of the remaining problems with the OLED technology is efficiency and colour saturation. The efficiency of OLED devices can be improved by doping the host organic layer with a suitable phosphorescent material in the emissive layer. We have synthesized a Schiff base zinc metal complex for OLEDs applications. Metal complex was characterized by FTIR, HNMR technique. PL emission spectra were recorded by keeping excitation wavelength fixed at 240 nm. A strong intense emission peak was observed at 410 nm. CIE chromaticity colour coordinates were observed at x =0.239 & y = 0.159. HOMO/LUMO energy gap were found to be -0.223 and -0.067 respectively for prepared zinc metal complex. It could be considered as a good light emitting phosphor material for possible application as emissive layer in OLEDs.

  5. Insights into aquatic toxicities of the antibiotics oxytetracycline and ciprofloxacin in the presence of metal: complexation versus mixture.

    PubMed

    Zhang, Yu; Cai, Xiyun; Lang, Xianming; Qiao, Xianliang; Li, Xuehua; Chen, Jingwen

    2012-07-01

    Co-contamination of ligand-like antibiotics (e.g., tetracyclines and quinolones) and heavy metals prevails in the environment, and thus the complexation between them is involved in environmental risks of antibiotics. To understand toxicological significance of the complex, effects of metal coordination on antibiotics' toxicity were investigated. The complexation of two antibiotics, oxytetracycline and ciprofloxacin, with three heavy metals, copper, zinc, and cadmium, was verified by spectroscopic techniques. The antibiotics bound metals via multiple coordination sites and rendered a mixture of various complexation speciations. Toxicity analysis indicated that metal coordination did modify the toxicity of the antibiotics and that antibiotic, metal, and their complex acted primarily as concentration addition. Comparison of EC(50) values revealed that the complex commonly was highest toxic and predominately correlated in toxicity to the mixture. Finally, environmental scenario analysis demonstrated that ignoring complexation would improperly classify environmental risks of the antibiotics. Copyright © 2012 Elsevier Ltd. All rights reserved.

  6. Preservation of NOM-metal complexes in a modern hyperalkaline stalagmite: Implications for speleothem trace element geochemistry

    NASA Astrophysics Data System (ADS)

    Hartland, Adam; Fairchild, Ian J.; Müller, Wolfgang; Dominguez-Villar, David

    2014-03-01

    We report the first quantitative study of the capture of colloidal natural organic matter (NOM) and NOM-complexed trace metals (V, Co, Cu, Ni) in speleothems. This study combines published NOM-metal dripwater speciation measurements with high-resolution laser ablation ICPMS (LA-ICPMS) and sub-annual stable isotope ratio (δ18O and δ13C), fluorescence and total organic carbon (TOC) analyses of a fast-growing hyperalkaline stalagmite (pH ˜11) from Poole’s Cavern, Derbyshire UK, which formed between 1997 and 2008 AD. We suggest that the findings reported here elucidate trace element variations arising from colloidal transport and calcite precipitation rate changes observed in multiple, natural speleothems deposited at ca. pH 7-8. We find that NOM-metal(aq) complexes on the boundary between colloidal and dissolved (˜1 nm diameter) show an annual cyclicity which is inversely correlated with the alkaline earth metals and is explained by calcite precipitation rate changes (as recorded by kinetically-fractionated stable isotopes). This relates to the strength of the NOM-metal complexation reaction, resulting in very strongly bound metals (Co in this system) essentially recording NOM co-precipitation (ternary complexation). More specifically, empirical partition coefficient (Kd) values between surface-reactive metals (V, Co, Cu, Ni) [expressed as ratio of trace element to Ca ratios in calcite and in solution] arise from variations in the ‘free’ fraction of total metal in aqueous solution (fm). Hence, differences in the preservation of each metal in calcite can be explained quantitatively by their complexation behaviour with aqueous NOM. Differences between inorganic Kd values and field measurements for metal partitioning into calcite occur where [free metal] ≪ [total metal] due to complexation reactions between metals and organic ligands (and potentially inorganic colloids). It follows that where fm ≈ 0, apparent inorganic Kd app values are also ≈0, but the

  7. 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

  8. Method for making conductors for ferrite memory arrays. [from pre-formed metal conductors

    NASA Technical Reports Server (NTRS)

    Heckler, C. H.; Baba, P. D.; Bhiwandker, N. C. (Inventor)

    1974-01-01

    The ferrite memory arrays are made from pre-formed metal conductors for the ferrite arrays. The conductors are made by forming a thin sheet of a metallizing paste of metal alloy powder, drying the paste layer, bisque firing the dried sheet at a first temperature, and then punching the conductors from the fired sheet. During the bisque firing, the conductor sheet shrinks to 58 percent of its pre-fired volume and the alloy particles sinter together. The conductors are embedded in ferrite sheet material and finally fired at a second higher temperature during which firing the conductors shrink approximately the same degree as the ferrite material.

  9. Infrared Photodissociation Spectroscopy of Metal Ion -WATER Complexes

    NASA Astrophysics Data System (ADS)

    Bandyopadhyay, B.; Carnegie, P. D.; Duncan, M. A.

    2011-06-01

    Metal ion-water complexes are produced in a supersonic expansion cluster source via laser vaporization technique. Infrared photodissociation spectroscopy has been performed in the O-H stretch region. DFT calculations have also been carried out to obtain the structures and vibrational frequencies. Infrared spectra show partially resolved rotational structures which will be analyzed.

  10. Electronic structure of transition metal-cysteine complexes from X-ray absorption spectroscopy.

    PubMed

    Leung, Bonnie O; Jalilehvand, Farideh; Szilagyi, Robert K

    2008-04-17

    The electronic structures of HgII, NiII, CrIII, and MoV complexes with cysteine were investigated by sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy and density functional theory. The covalency in the metal-sulfur bond was determined by analyzing the intensities of the electric-dipole allowed pre-edge features appearing in the XANES spectra below the ionization threshold. Because of the well-defined structures of the selected cysteine complexes, the current work provides a reference set for further sulfur K-edge XAS studies of bioinorganic active sites with transition metal-sulfur bonds from cysteine residues as well as more complex coordination compounds with thiolate ligands.

  11. Complex transition metal hydrides: linear correlation of countercation electronegativity versus T-D bond lengths.

    PubMed

    Humphries, T D; Sheppard, D A; Buckley, C E

    2015-06-30

    For homoleptic 18-electron complex hydrides, an inverse linear correlation has been established between the T-deuterium bond length (T = Fe, Co, Ni) and the average electronegativity of the metal countercations. This relationship can be further employed towards aiding structural solutions and predicting physical properties of novel complex transition metal hydrides.

  12. Tensile strength of composite sheets with unidirectional stringers and crack-like damage

    NASA Technical Reports Server (NTRS)

    Poe, C. C., Jr.

    1984-01-01

    The damage tolerance characteristics of metal tension panels with riveted and bonded stringers are well known. The stringers arrest unstable cracks and retard propagation of fatigue cracks. Residual strengths and fatigue lives are considerably greater than those of unstiffened or integrally stiffened sheets. The damage tolerance of composite sheets with bonded composite stringers loaded in tension was determined. Cracks in composites do not readily propagate in fatigue, at least not through fibers. Moreover, the residual strength of notched composites is sometimes even increased by fatigue loading. Therefore, the residual strength aspect of damage tolerance, and not fatigue crack propagation, was investigated. About 50 graphite/epoxy composite panels were made with two sheet layups and several stringer configurations. Crack-like slots were cut in the middle of the panels to simulate damage. The panels were instrumented and monotonically loaded in tension to failure. The tests indicate that the composite panels have considerable damage tolerance, much like metal panels. The stringers arrested cracks that ran from the crack-like slots, and the residual strengths were considerably greater than those of unstiffened composite sheets. A stress intensity factor analysis was developed to predict the failing strains of the stiffened panels. Using the analysis, a single design curve was produced for composite sheets with bonded stringers of any configuration.

  13. Peptide-mediated vectorization of metal complexes: conjugation strategies and biomedical applications.

    PubMed

    Soler, Marta; Feliu, Lidia; Planas, Marta; Ribas, Xavi; Costas, Miquel

    2016-08-16

    The rich chemical and structural versatility of transition metal complexes provides numerous novel paths to be pursued in the design of molecules that exert particular chemical or physicochemical effects that could operate over specific biological targets. However, the poor cell permeability of metallodrugs represents an important barrier for their therapeutic use. The conjugation between metal complexes and a functional peptide vector can be regarded as a versatile and potential strategy to improve their bioavailability and accumulation inside cells, and the site selectivity of their effect. This perspective lies in reviewing the recent advances in the design of metallopeptide conjugates for biomedical applications. Additionally, we highlight the studies where this approach has been directed towards the incorporation of redox active metal centers into living organisms for modulating the cellular redox balance, as a tool with application in anticancer therapy.

  14. Metal phthalocyanine polymers

    NASA Technical Reports Server (NTRS)

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

    1984-01-01

    Metal 4, 4', 4", 4"'=tetracarboxylic phthalocyanines (MPTC) are prepared by reaction of trimellitic anhydride, a salt or hydroxide of the desired metal (or the metal in powdered form), urea and a catalyst. A purer form of MPTC is prepared than heretofore. These tetracarboxylic acids are then polymerized by heat to sheet polymers which have superior heat and oxidation resistance. The metal is preferably a divalent metal having an atomic radius close to 1.35A.

  15. Supramolecular control of transition metal complexes in water by a hydrophobic cavity: a bio-inspired strategy.

    PubMed

    Bistri, Olivia; Reinaud, Olivia

    2015-03-14

    Supramolecular chemistry in water is a very challenging research area. In biology, water is the universal solvent where transition metal ions play major roles in molecular recognition and catalysis. In enzymes, it participates in substrate binding and/or activation in the heart of a pocket defined by the folded protein. The association of a hydrophobic cavity with a transition metal ion is thus a very appealing strategy for controlling the metal ion properties in the very competitive water solvent. Various systems based on intrinsically water-soluble macrocyclic structures such as cyclodextrins, cucurbituryls, and metallo-cages have been reported. Others use calixarenes and resorcinarenes functionalized with hydrophilic substituents. One approach for connecting a metal complex to these cavities is to graft a ligand for metal ion binding at their edge. Early work with cyclodextrins has shown Michaelis-Menten like catalysis displaying enhanced kinetics and substrate-selectivity. Remarkable examples of regio- and stereo-selective transformation of substrates have been reported as well. Dynamic two-phase systems for transition metal catalysis have also been developed. They rely on either water-transfer of the metal complex through ligand embedment or synergistic coordination of a metal ion and substrate hosting. Another strategy consists in using metallo-cages, which provide a well-defined hydrophobic space, to stabilize metal complexes in water. When the cages can host simultaneously a substrate and a reactive metal complex, size- and regio-selective catalysis was obtained. Finally, construction of a polydentate coordination site closely interlocked with a calixarene or resorcinarene macrocycle has been shown to be a very fruitful strategy for obtaining metal complexes with remarkable hosting properties. For each of these systems, the synergism resulting from the biomimetic association of a hydrophobic cavity and a metal ion is discussed within the objective of

  16. Optimization of Surface Roughness and Wall Thickness in Dieless Incremental Forming Of Aluminum Sheet Using Taguchi

    NASA Astrophysics Data System (ADS)

    Hamedon, Zamzuri; Kuang, Shea Cheng; Jaafar, Hasnulhadi; Azhari, Azmir

    2018-03-01

    Incremental sheet forming is a versatile sheet metal forming process where a sheet metal is formed into its final shape by a series of localized deformation without a specialised die. However, it still has many shortcomings that need to be overcome such as geometric accuracy, surface roughness, formability, forming speed, and so on. This project focus on minimising the surface roughness of aluminium sheet and improving its thickness uniformity in incremental sheet forming via optimisation of wall angle, feed rate, and step size. Besides, the effect of wall angle, feed rate, and step size to the surface roughness and thickness uniformity of aluminium sheet was investigated in this project. From the results, it was observed that surface roughness and thickness uniformity were inversely varied due to the formation of surface waviness. Increase in feed rate and decrease in step size will produce a lower surface roughness, while uniform thickness reduction was obtained by reducing the wall angle and step size. By using Taguchi analysis, the optimum parameters for minimum surface roughness and uniform thickness reduction of aluminium sheet were determined. The finding of this project helps to reduce the time in optimising the surface roughness and thickness uniformity in incremental sheet forming.

  17. Experimental investigation of a 1 kA/cm² sheet beam plasma cathode electron gun.

    PubMed

    Kumar, Niraj; Pal, Udit Narayan; Pal, Dharmendra Kumar; Prajesh, Rahul; Prakash, Ram

    2015-01-01

    In this paper, a cold cathode based sheet-beam plasma cathode electron gun is reported with achieved sheet-beam current density ∼1 kA/cm(2) from pseudospark based argon plasma for pulse length of ∼200 ns in a single shot experiment. For the qualitative assessment of the sheet-beam, an arrangement of three isolated metallic-sheets is proposed. The actual shape and size of the sheet-electron-beam are obtained through a non-conventional method by proposing a dielectric charging technique and scanning electron microscope based imaging. As distinct from the earlier developed sheet beam sources, the generated sheet-beam has been propagated more than 190 mm distance in a drift space region maintaining sheet structure without assistance of any external magnetic field.

  18. 25. VIEW TO NORTHWEST, ENGINE PUMP EXTENSION, DETAIL OF SHEET ...

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

    25. VIEW TO NORTHWEST, ENGINE PUMP EXTENSION, DETAIL OF SHEET METAL MOLDING TO OPENING BETWEEN ENGINE/PUMP HOUSE AND ENGINE/PUMP HOUSE EXTENSION - Deer Island Pumping Station, Boston, Suffolk County, MA

  19. New trends in the optical and electronic applications of polymers containing transition-metal complexes.

    PubMed

    Liu, Shu-Juan; Chen, Yang; Xu, Wen-Juan; Zhao, Qiang; Huang, Wei

    2012-04-13

    Polymers containing transition-metal complexes exhibit excellent optical and electronic properties, which are different from those of polymers with a pure organic skeleton and combine the advantages of both polymers and metal complexes. Hence, research about this class of polymers has attracted more and more interest in recent years. Up to now, a number of novel polymers containing transition-metal complexes have been exploited, and significant advances in their optical and electronic applications have been achieved. In this article, we summarize some new research trends in the applications of this important class of optoelectronic polymers, such as chemo/biosensors, electronic memory devices and photovoltaic devices. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Material damage modeling and detection in a thin metallic sheet and sandwich panel using passive acoustic transmission

    NASA Astrophysics Data System (ADS)

    Jiang, Hao

    A method is developed for modeling, detecting, and locating material damage in homogeneous thin metallic sheets and sandwich panels. Analytical and numerical models are used along with non-contact, passive acoustic transmission measurements. It is shown that global and local damage mechanisms characterized by both material and geometrical changes in structural components can be detected using passive acoustic transmission measurements. Theoretical models of a flat sheet and sandwich panel are developed to describe the effects of global material damage due to density, modulus, or thickness changes on backplane radiated sound pressure level distributions. To describe the effects of local material damage, a three-segment stepped beam model and finite element beam, plate, and sandwich panel models are developed and analyzed using the acoustic transmission approach. It is shown that increases or decreases in transmitted sound energy occur behind a damaged material component that exhibits changes in thickness or other geometric or material properties. The damage due to thickness and density changes can be detected from the acoustic transmission, but modulus changes cannot. If the damage is located at an anti-node of a certain forced vibration pattern, the damage can be more readily observed in the data. Higher excitation frequencies within the operating spectrum are preferred to lower frequencies for damage detection. With the finite element beam, plate, and sandwich panel models, local damage detection has been performed in simulations. Experiments on a baffled homogeneous sheet and sandwich panel subjected to broadband acoustic energy show that transmitted intensity measurements with non-contact probes can be used to identify and locate material defects in the sheet and sandwich panel. Material damage is most readily identified where the changes in transmitted sound intensity are largest in the resonant frequency range of the panel. The three main contributions of this

  1. Gas phase reactions of doubly charged alkaline earth and transition metal(II)-ligand complexes generated by electrospray ionization

    NASA Astrophysics Data System (ADS)

    Kohler, Martin; Leary, Julie A.

    1997-03-01

    Doubly charged metal(II)-complexes of [alpha] 1-3, [alpha] 1-6 mannotriose and the conserved trimannosyl core pentasaccharide as well as doubly charged complexes of Co(II), Mn(II), Ca(II) and Sr(II) with acetonitrile generated by electrospray ionization were studied by low energy collision induced dissociation (CID). Two main fragmentation pathways were observed for the metal(II)-oligosaccharide complexes. Regardless of the coordinating metal, loss of a neutral dehydrohexose residue (162 Da) from the doubly charged precursor ion is observed, forming a doubly charged product ion. However, if the oligosaccharide is coordinated to Co(II) or Mn(II), loss of a dehydroxyhexose cation is also observed. Investigation of the low mass region of the mass spectra of the metal coordinated oligosaccharides revealed intense signals corresponding to [metal(II) + (CH3CN)n2+ (where n = 1-6) species which were being formed by the metal(II) ions and the acetonitrile present in the sample. Analysis of these metal(II)-acetonitrile complexes provided further insight into the processes occurring upon low energy CID of doubly charged metal complexes. The metal(II)-acetonitrile system showed neutral loss and ligand cleavage as observed with the oligosaccharide complexes, as well as a series of six different dissociation mechanisms, most notable among them reduction from [metal(II) + (CH3CN)n2+ to the bare [metal(I)]+ species by electron transfer. Depending on the metal and collision gas chosen, one observes electron transfer from the ligand to the metal, electron transfer from the collision gas to the metal, proton transfer between ligands, heterolytic cleavage of the ligands, reactive collisions and loss of neutral ligands.

  2. Prediction of stress- and strain-based forming limits of automotive thin sheets by numerical, theoretical and experimental methods

    NASA Astrophysics Data System (ADS)

    Béres, Gábor; Weltsch, Zoltán; Lukács, Zsolt; Tisza, Miklós

    2018-05-01

    Forming limit is a complex concept of limit values related to the onset of local necking in the sheet metal. In cold sheet metal forming, major and minor limit strains are influenced by the sheet thickness, strain path (deformation history) as well as material parameters and microstructure. Forming Limit Curves are plotted in ɛ1 - ɛ2 coordinate system providing the classic strain-based Forming Limit Diagram (FLD). Using the appropriate constitutive model, the limit strains can be changed into the stress-based Forming Limit Diagram (SFLD), irrespective of the strain path. This study is about the effect of the hardening model parameters on defining of limit stress values during Nakazima tests for automotive dual phase (DP) steels. Five limit strain pairs were specified experimentally with the loading of five different sheet geometries, which performed different strain-paths from pure shear (-2ɛ2=ɛ1) up to biaxial stretching (ɛ2=ɛ1). The former works of Hill, Levy-Tyne and Keeler-Brazier made possible some kind of theoretical strain determination, too. This was followed by the stress calculation based on the experimental and theoretical strain data. Since the n exponent in the Nádai expression is varying with the strain at some DP steels, we applied the least-squares method to fit other hardening model parameters (Ludwik, Voce, Hockett-Sherby) to calculate the stress fields belonging to each limit strains. The results showed that each model parameters could produce some discrepancies between the limit stress states in the range of higher equivalent strains than uniaxial stretching. The calculated hardening models were imported to FE code to extend and validate the results by numerical simulations.

  3. Parameter optimization and stretch enhancement of AISI 316 sheet using rapid prototyping technique

    NASA Astrophysics Data System (ADS)

    Moayedfar, M.; Rani, A. M.; Hanaei, H.; Ahmad, A.; Tale, A.

    2017-10-01

    Incremental sheet forming is a flexible manufacturing process which uses the indenter point-to-point force to shape the sheet metal workpiece into manufactured parts in batch production series. However, the problem sometimes arising from this process is the low plastic point in the stress-strain diagram of the material which leads the low stretching amount before ultra-tensile strain point. Hence, a set of experiments is designed to find the optimum forming parameters in this process for optimum sheet thickness distribution while both sides of the sheet are considered for the surface quality improvement. A five-axis high-speed CNC milling machine is employed to deliver the proper motion based on the programming system while the clamping system for holding the sheet metal was a blank mould. Finally, an electron microscope and roughness machine are utilized to evaluate the surface structure of final parts, illustrate any defect may cause during the forming process and examine the roughness of the final part surface accordingly. The best interaction between parameters is obtained with the optimum values which lead the maximum sheet thickness distribution of 4.211e-01 logarithmic elongation when the depth was 24mm with respect to the design. This study demonstrates that this rapid forming method offers an alternative solution for surface quality improvement of 65% avoiding the low probability of cracks and low probability of crystal structure changes.

  4. Metallic nanomesh

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ren, Zhifeng; Sun, Tianyi; Guo, Chuanfei

    2018-02-20

    A transparent flexible nanomesh having at least one conductive element and sheet resistance less than 300.OMEGA./.quadrature. when stretched to a strain of 200% in at least one direction. The nanomesh is formed by depositing a sacrificial film, depositing, etching, and oxidizing a first metal layer on the film, etching the sacrificial film, depositing a second metal layer, and removing the first metal layer to form a nanomesh on the substrate.

  5. Synthesis and Properties of "Sandwich" Diimine-Coinage Metal Ethylene Complexes.

    PubMed

    Klimovica, Kristine; Kirschbaum, Kristin; Daugulis, Olafs

    2016-09-12

    Synthesis and full characterization of cationic isostructural "sandwich" diimine-coinage metal ethylene complexes are reported. Ethylene self-exchange kinetics proceeds by an associative exchange mechanism for Cu and Au complexes. The fastest ligand exchange was observed for Ag complex 8a . The upper limit of Δ G ‡ , assuming associative ligand exchange, was found to be ca. 5.0 kcal/mol. Ethylene self-exchange in Cu complex 7b proceeds with Δ G 298 ‡ = 12.9 ± 0.1 kcal/mol, while the exchange is the slowest in Au complex 9 , with Δ G 298 ‡ = 16.7 ± 0.1 kcal/mol. Copper complex 7b is unusually stable and can survive in air for years.

  6. Structure-activity relationships of mononuclear metal-thiosemicarbazone complexes endowed with potent antiplasmodial and antiamoebic activities.

    PubMed

    Bahl, Deepa; Athar, Fareeda; Soares, Milena Botelho Pereira; de Sá, Matheus Santos; Moreira, Diogo Rodrigo Magalhães; Srivastava, Rajendra Mohan; Leite, Ana Cristina Lima; Azam, Amir

    2010-09-15

    A useful concept for the rational design of antiparasitic drug candidates is the complexation of bioactive ligands with transition metals. In view of this, an investigation was conducted into a new set of metal complexes as potential antiplasmodium and antiamoebic agents, in order to examine the importance of metallic atoms, as well as the kind of sphere of co-ordination, in these biological properties. Four functionalized furyl-thiosemicarbazones (NT1-4) treated with divalent metals (Cu, Co, Pt, and Pd) to form the mononuclear metallic complexes of formula [M(L)2Cl2] or [M(L)Cl2] were examined. The pharmacological characterization, including assays against Plasmodium falciparum and Entamoeba histolytica, cytotoxicity to mammalian cells, and interaction with pBR 322 plasmid DNA was performed. Structure-activity relationship data revealed that the metallic complexation plays an essential role in antiprotozoal activity, rather than the simple presence of the ligand or metal alone. Important steps towards identification of novel antiplasmodium (NT1Cu, IC50 of 4.6 microM) and antiamoebic (NT2Pd, IC50 of 0.6 microM) drug prototypes were achieved. Of particular relevance to this work, these prototypes were able to reduce the proliferation of these parasites at concentrations that are not cytotoxic to mammalian cells. Copyright (c) 2010. Published by Elsevier Ltd.

  7. Designed topology and site-selective metal composition in tetranuclear [MM'...M'M] linear complexes.

    PubMed

    Barrios, Leoní A; Aguilà, David; Roubeau, Olivier; Gamez, Patrick; Ribas-Ariño, Jordi; Teat, Simon J; Aromí, Guillem

    2009-10-26

    The ligand 1,3-bis[3-oxo-3-(2-hydroxyphenyl)propionyl]benzene (H(4)L), designed to align transition metals into tetranuclear linear molecules, reacts with M(II) salts (M=Ni, Co, Cu) to yield complexes with the expected [MMMM] topology. The novel complexes [Co(4)L(2)(py)(6)] (2; py=pyridine) and [Na(py)(2)][Cu(4)L(2)(py)(4)](ClO(4)) (3) have been crystallographically characterised. The metal sites in complexes 2 and 3, together with previously characterised [Ni(4)L(2)(py)(6)] (1), favour different coordination geometries. These have been exploited for the deliberate synthesis of the heterometallic complex [Cu(2)Ni(2)L(2)(py)(6)] (4). Complexes 1, 2, 3 and 4 exhibit antiferromagnetic interactions between pairs of metals within each cluster, leading to S=0 spin ground states, except for the latter cluster, which features two quasi-independent S=1/2 moieties within the molecule. Complex 4 gathers the structural and physical conditions, thus allowing it to be considered as prototype of a two-qbit quantum gate.

  8. Oxalate metal complexes in aerosol particles: implications for the hygroscopicity of oxalate-containing particles

    NASA Astrophysics Data System (ADS)

    Furukawa, T.; Takahashi, Y.

    2011-05-01

    Atmospheric aerosols have both a direct and an indirect cooling effect that influences the radiative balance at the Earth's surface. It has been estimated that the degree of cooling is large enough to weaken the warming effect of carbon dioxide. Among the cooling factors, secondary organic aerosols (SOA) play an important role in the solar radiation balance in the troposphere as SOA can act as cloud condensation nuclei (CCN) and extend the lifespan of clouds because of their high hygroscopic and water soluble nature. Oxalic acid is an important component of SOA, and is produced via several formation pathways in the atmosphere. However, it is not certain whether oxalic acid exists as free oxalic acid or as metal oxalate complexes in aerosols, although there is a marked difference in their solubility in water and their hygroscopicity. We employed X-ray absorption fine structure spectroscopy to characterize the calcium (Ca) and zinc (Zn) in aerosols collected at Tsukuba in Japan. Size-fractionated aerosol samples were collected for this purpose using an impactor aerosol sampler. It was shown that 10-60% and 20-100% of the total Ca and Zn in the finer particles (<2.1 μm) were present as Ca and Zn oxalate complexes, respectively. Oxalic acid is hygroscopic and can thus increase the CCN activity of aerosol particles, while complexes with various polyvalent metal ions such as Ca and Zn are not hygroscopic, which cannot contribute to the increase of the CCN activity of aerosols. Based on the concentrations of noncomplexed and metal-complexed oxalate species, we found that most of the oxalic acid is present as metal oxalate complexes in the aerosols, suggesting that oxalic acid does not always increase the hygroscopicity of aerosols in the atmosphere. Similar results are expected for other dicarboxylic acids, such as malonic and succinic acids. Thus, it is advisable that the cooling effect of organic aerosols should be estimated by including the information on metal

  9. Continuous Processing of High Thermal Conductivity Polyethylene Fibers and Sheets

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    None

    2016-12-01

    This factsheet describes a project that developed a new, continuous manufacturing process to make high molecular weight, high thermal conductivity polyethylene fibers and sheets to replace metals and ceramics in heat transfer applications.

  10. Complex furrows in a 2D epithelial sheet code the 3D structure of a beetle horn.

    PubMed

    Matsuda, Keisuke; Gotoh, Hiroki; Tajika, Yuki; Sushida, Takamichi; Aonuma, Hitoshi; Niimi, Teruyuki; Akiyama, Masakazu; Inoue, Yasuhiro; Kondo, Shigeru

    2017-10-24

    The external organs of holometabolous insects are generated through two consecutive processes: the development of imaginal primordia and their subsequent transformation into the adult structures. During the latter process, many different phenomena at the cellular level (e.g. cell shape changes, cell migration, folding and unfolding of epithelial sheets) contribute to the drastic changes observed in size and shape. Because of this complexity, the logic behind the formation of the 3D structure of adult external organs remains largely unknown. In this report, we investigated the metamorphosis of the horn in the Japanese rhinoceros beetle Trypoxylus dichotomus. The horn primordia is essentially a 2D epithelial cell sheet with dense furrows. We experimentally unfolded these furrows using three different methods and found that the furrow pattern solely determines the 3D horn structure, indicating that horn formation in beetles occurs by two distinct processes: formation of the furrows and subsequently unfolding them. We postulate that this developmental simplicity offers an inherent advantage to understanding the principles that guide 3D morphogenesis in insects.

  11. Dialkyldiselenophosphinato-metal complexes - a new class of single source precursors for deposition of metal selenide thin films and nanoparticles

    NASA Astrophysics Data System (ADS)

    Malik, Sajid N.; Akhtar, Masood; Revaprasadu, Neerish; Qadeer Malik, Abdul; Azad Malik, Mohammad

    2014-08-01

    We report here a new synthetic approach for convenient and high yield synthesis of dialkyldiselenophosphinato-metal complexes. A number of diphenyldiselenophosphinato-metal as well as diisopropyldiselenophosphinato-metal complexes have been synthesized and used as precursors for deposition of semiconductor thin films and nanoparticles. Cubic Cu2-xSe and tetragonal CuInSe2 thin films have been deposited by AACVD at 400, 450 and 500 °C whereas cubic PbSe and tetragonal CZTSe thin films have been deposited through doctor blade method followed by annealing. SEM investigations revealed significant differences in morphology of the films deposited at different temperatures. Preparation of Cu2-xSe and In2Se3 nanoparticles using diisopropyldiselenophosphinato-metal precursors has been carried out by colloidal method in HDA/TOP system. Cu2-xSe nanoparticles (grown at 250 °C) and In2Se3 nanoparticles (grown at 270 °C) have a mean diameter of 5.0 ± 1.2 nm and 13 ± 2.5 nm, respectively.

  12. Divalent Metal-Ion Complexes with Dipeptide Ligands Having Phe and His Side-Chain Anchors: Effects of Sequence, Metal Ion, and Anchor.

    PubMed

    Dunbar, Robert C; Berden, Giel; Martens, Jonathan K; Oomens, Jos

    2015-09-24

    Conformational preferences have been surveyed for divalent metal cation complexes with the dipeptide ligands AlaPhe, PheAla, GlyHis, and HisGly. Density functional theory results for a full set of complexes are presented, and previous experimental infrared spectra, supplemented by a number of newly recorded spectra obtained with infrared multiple photon dissociation spectroscopy, provide experimental verification of the preferred conformations in most cases. The overall structural features of these complexes are shown, and attention is given to comparisons involving peptide sequence, nature of the metal ion, and nature of the side-chain anchor. A regular progression is observed as a function of binding strength, whereby the weakly binding metal ions (Ba(2+) to Ca(2+)) transition from carboxylate zwitterion (ZW) binding to charge-solvated (CS) binding, while the stronger binding metal ions (Ca(2+) to Mg(2+) to Ni(2+)) transition from CS binding to metal-ion-backbone binding (Iminol) by direct metal-nitrogen bonds to the deprotonated amide nitrogens. Two new sequence-dependent reversals are found between ZW and CS binding modes, such that Ba(2+) and Ca(2+) prefer ZW binding in the GlyHis case but prefer CS binding in the HisGly case. The overall binding strength for a given metal ion is not strongly dependent on the sequence, but the histidine peptides are significantly more strongly bound (by 50-100 kJ mol(-1)) than the phenylalanine peptides.

  13. Sol-Gel-Synthesis of Nanoscopic Complex Metal Fluorides

    PubMed Central

    Rehmer, Alexander; Scheurell, Kerstin; Scholz, Gudrun; Kemnitz, Erhard

    2017-01-01

    The fluorolytic sol-gel synthesis for binary metal fluorides (AlF3, CaF2, MgF2) has been extended to ternary and quaternary alkaline earth metal fluorides (CaAlF5, Ca2AlF7, LiMgAlF6). The formation and crystallization of nanoscopic ternary CaAlF5 and Ca2AlF7 sols in ethanol were studied by 19F liquid and solid state NMR (nuclear magnetic resonance) spectroscopy, as well as transmission electron microscopy (TEM). The crystalline phases of the annealed CaAlF5, Ca2AlF7, and LiMgAlF6 xerogels between 500 and 700 °C could be determined by X-ray powder diffraction (XRD) and 19F solid state NMR spectroscopy. The thermal behavior of un-annealed nanoscopic ternary and quaternary metal fluoride xerogels was ascertained by thermal analysis (TG/DTA). The obtained crystalline phases of CaAlF5 and Ca2AlF7 derived from non-aqueous sol-gel process were compared to crystalline phases from the literature. The corresponding nanoscopic complex metal fluoride could provide a new approach in ceramic and luminescence applications. PMID:29099086

  14. Deep drawability of Ti/resin/Ti laminated sheet

    NASA Astrophysics Data System (ADS)

    Hardada, Yasunroi; Hattori, Shuji

    2017-10-01

    Aiming to enhance functionality of titanium cup, the formability of titanium/resin/titanium laminated sheet by deep drawing was investigated. Although pure titanium has excellent corrosion resistance, the density of titanium is higher than that of light metals, such as aluminum and magnesium. Part of the titanium cup made of resin allows for weight reduction of the cup. Furthermore, the clad cup is more likely to have heat retention and protection against vibration characteristics. In the experiment, the materials were pure titanium and polycarbonate. The initial thickness of the sheet was 0.2 to 0.5 mm in thickness. A total plate thickness of the blank was 1.0 to 1.5 mm in thickness. The blank diameter is 70 mm. The laminated sheet was constituted by interposing resin between two titanium sheets. Each sheet in stacked condition was not joined each other. In the deep drawing process, the laminated sheet was employed and a flat sheet blank was formed into a circle by a punch. For the prevention of seizure in contact area between a drawing tool and titanium, titanium blank was treated by oxide coating. By this method, the fresh and clean titanium is not in direct contact with the die during the forming due to the existence of the oxide layer. The deep drawing was carried out to investigate the formability. The laminated sheet was successfully drawn without the cracks. The section of the drawn cup was observed to examine a formability of the resin sheet. The reduction rate of the thickness was less than 10%. It was found that the titanium/resin/titanium clad cup was successfully drawn.

  15. PRODUCTION OF SHEET FROM PARTICULATE MATERIAL

    DOEpatents

    Blainey, A.

    1959-05-12

    A process is presented for forming coherent sheet material from particulate material such as granular or powdered metal, granular or powdered oxide, slurries, pastes, and plastic mixes which cohere under pressure. The primary object is to avoid the use of expensive and/ or short lived pressing tools, that is, dies and specially profiled rolls, and so to reduce the cost of the product and to prcvide in a simple manner for the making of the product in a variety of shapes or sizes. The sheet material is formed when the particulate material is laterally confined in a boundary material deformable in all lateral directions under axial pressure and then axially compressing the layer of particulate material together with the boundary material.

  16. General Synthesis of Transition-Metal Oxide Hollow Nanospheres/Nitrogen-Doped Graphene Hybrids by Metal-Ammine Complex Chemistry for High-Performance Lithium-Ion Batteries.

    PubMed

    Chen, Jiayuan; Wu, Xiaofeng; Gong, Yan; Wang, Pengfei; Li, Wenhui; Mo, Shengpeng; Peng, Shengpan; Tan, Qiangqiang; Chen, Yunfa

    2018-02-09

    We present a general and facile synthesis strategy, on the basis of metal-ammine complex chemistry, for synthesizing hollow transition-metal oxides (Co 3 O 4 , NiO, CuO-Cu 2 O, and ZnO)/nitrogen-doped graphene hybrids, potentially applied in high-performance lithium-ion batteries. The oxygen-containing functional groups of graphene oxide play a prerequisite role in the formation of hollow transition-metal oxides on graphene nanosheets, and a significant hollowing process occurs only when forming metal (Co 2+ , Ni 2+ , Cu 2+ , or Zn 2+ )-ammine complex ions. Moreover, the hollowing process is well correlated with the complexing capacity between metal ions and NH 3 molecules. The significant hollowing process occurs for strong metal-ammine complex ions including Co 2+ , Ni 2+ , Cu 2+ , and Zn 2+ ions, and no hollow structures formed for weak and/or noncomplex Mn 2+ and Fe 3+ ions. Simultaneously, this novel strategy can also achieve the direct doping of nitrogen atoms into the graphene framework. The electrochemical performance of two typical hollow Co 3 O 4 or NiO/nitrogen-doped graphene hybrids was evaluated by their use as anodic materials. It was demonstrated that these unique nanostructured hybrids, in contrast with the bare counterparts, solid transition-metal oxides/nitrogen-doped graphene hybrids, perform with significantly improved specific capacity, superior rate capability, and excellent capacity retention. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Microstructure and Mechanical Performance of Friction Stir Spot-Welded Aluminum-5754 Sheets

    NASA Astrophysics Data System (ADS)

    Pathak, N.; Bandyopadhyay, K.; Sarangi, M.; Panda, Sushanta Kumar

    2013-01-01

    Friction stir spot welding (FSSW) is a recent trend of joining light-weight sheet metals while fabricating automotive and aerospace body components. For the successful application of this solid-state welding process, it is imperative to have a thorough understanding of the weld microstructure, mechanical performance, and failure mechanism. In the present study, FSSW of aluminum-5754 sheet metal was tried using tools with circular and tapered pin considering different tool rotational speeds, plunge depths, and dwell times. The effects of tool design and process parameters on temperature distribution near the sheet-tool interface, weld microstructure, weld strength, and failure modes were studied. It was found that the peak temperature was higher while welding with a tool having circular pin compared to tapered pin, leading to a bigger dynamic recrystallized stir zone (SZ) with a hook tip bending towards the upper sheet and away from the keyhole. Hence, higher lap shear separation load was observed in the welds made from circular pin compared to those made from tapered pin. Due to influence of size and hardness of SZ on crack propagation, three different failure modes of weld nugget were observed through optical cross-sectional micrograph and SEM fractographs.

  18. Characterization of tannin-metal complexes by UV-visible spectrophotometry

    USDA-ARS?s Scientific Manuscript database

    Tannins enter soils by plant decay and rain throughfall, but little is known of their effects on soils. Tannins may influence bioavailability and toxicity of metals by forming complexes and by mediating redox reactions. We evaluated the affinity and stoichiometry of Al(III) for a gallotannin, pent...

  19. 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

  20. Solvation Effect on Complexation of Alkali Metal Cations by a Calix[4]arene Ketone Derivative.

    PubMed

    Požar, Josip; Nikšić-Franjić, Ivana; Cvetnić, Marija; Leko, Katarina; Cindro, Nikola; Pičuljan, Katarina; Borilović, Ivana; Frkanec, Leo; Tomišić, Vladislav

    2017-09-14

    The medium effect on the complexation of alkali metal cations with a calix[4]arene ketone derivative (L) was systematically examined in methanol, ethanol, N-methylformamide, N,N-dimethylformamide, dimethyl sulfoxide, and acetonitrile. In all solvents the binding of Na + cation by L was rather efficient, whereas the complexation of other alkali metal cations was observed only in methanol and acetonitrile. Complexation reactions were enthalpically controlled, while ligand dissolution was endothermic in all cases. A notable influence of the solvent on NaL + complex stability could be mainly attributed to the differences in complexation entropies. The higher NaL + stability in comparison to complexes with other alkali metal cations in acetonitrile was predominantly due to a more favorable complexation enthalpy. The 1 H NMR investigations revealed a relatively low affinity of the calixarene sodium complex for inclusion of the solvent molecule in the calixarene hydrophobic cavity, with the exception of acetonitrile. Differences in complex stabilities in the explored solvents, apart from N,N-dimethylformamide and acetonitrile, could be mostly explained by taking into account solely the cation and complex solvation. A considerable solvent effect on the complexation equilibria was proven to be due to an interesting interplay between the transfer enthalpies and entropies of the reactants and the complexes formed.

  1. Complexing agent and heavy metal removals from metal plating effluent by electrocoagulation with stainless steel electrodes.

    PubMed

    Kabdaşli, Işik; Arslan, Tülin; Olmez-Hanci, Tuğba; Arslan-Alaton, Idil; Tünay, Olcay

    2009-06-15

    In the present study, the treatability of a metal plating wastewater containing complexed metals originating from the nickel and zinc plating process by electrocoagulation using stainless steel electrodes was experimentally investigated. The study focused on the effect of important operation parameters on electrocoagulation process performance in terms of organic complex former, nickel and zinc removals as well as sludge production and specific energy consumption. The results indicated that increasing the applied current density from 2.25 to 9.0 mA/cm(2) appreciably enhanced TOC removal efficiency from 20% to 66%, but a further increase in the applied current density to 56.25 mA/cm(2) did not accelerate TOC removal rates. Electrolyte concentration did not affect the process performance significantly and the highest TOC reduction (66%) accompanied with complete heavy metal removals were achieved at the original chloride content ( approximately 1500 mg Cl/L) of the wastewater sample. Nickel removal performance was adversely affected by the decrease of initial pH from its original value of 6. Optimum working conditions for electrocoagulation of metal plating effluent were established as follows: an applied current density of 9 mA/cm(2), the effluent's original electrolyte concentration and pH of the composite sample. TOC removal rates obtained for all electrocoagulation runs fitted pseudo-first-order kinetics very well (R(2)>92-99).

  2. Applicability study of classical and contemporary models for effective complex permittivity of metal powders.

    PubMed

    Kiley, Erin M; Yakovlev, Vadim V; Ishizaki, Kotaro; Vaucher, Sebastien

    2012-01-01

    Microwave thermal processing of metal powders has recently been a topic of a substantial interest; however, experimental data on the physical properties of mixtures involving metal particles are often unavailable. In this paper, we perform a systematic analysis of classical and contemporary models of complex permittivity of mixtures and discuss the use of these models for determining effective permittivity of dielectric matrices with metal inclusions. Results from various mixture and core-shell mixture models are compared to experimental data for a titanium/stearic acid mixture and a boron nitride/graphite mixture (both obtained through the original measurements), and for a tungsten/Teflon mixture (from literature). We find that for certain experiments, the average error in determining the effective complex permittivity using Lichtenecker's, Maxwell Garnett's, Bruggeman's, Buchelnikov's, and Ignatenko's models is about 10%. This suggests that, for multiphysics computer models describing the processing of metal powder in the full temperature range, input data on effective complex permittivity obtained from direct measurement has, up to now, no substitute.

  3. Determining the magnitude and direction of photoinduced ligand field switching in photochromic metal-organic complexes: molybdenum-tetracarbonyl spirooxazine complexes.

    PubMed

    Paquette, Michelle M; Patrick, Brian O; Frank, Natia L

    2011-07-06

    The ability to optically switch or tune the intrinsic properties of transition metals (e.g., redox potentials, emission/absorption energies, and spin states) with photochromic metal-ligand complexes is an important strategy for developing "smart" materials. We have described a methodology for using metal-carbonyl complexes as spectroscopic probes of ligand field changes associated with light-induced isomerization of photochromic ligands. Changes in ligand field between the ring-closed spirooxazine (SO) and ring-opened photomerocyanine (PMC) forms of photochromic azahomoadamantyl and indolyl phenanthroline-spirooxazine ligands are demonstrated through FT-IR, (13)C NMR, and computational studies of their molybdenum-tetracarbonyl complexes. The frontier molecular orbitals (MOs) of the SO and PMC forms differ considerably in both electron density distributions and energies. Of the multiple π* MOs in the SO and PMC forms of the ligands, the LUMO+1, a pseudo-b(1)-symmetry phenanthroline-based MO, mixes primarily with the Mo(CO)(4) fragment and provides the major pathway for Mo(d)→phen(π*) backbonding. The LUMO+1 is found to be 0.2-0.3 eV lower in energy in the SO form relative to the PMC form, suggesting that the SO form is a better π-acceptor. Light-induced isomerization of the photochromic ligands was therefore found to lead to changes in the energies of their frontier MOs, which in turn leads to changes in π-acceptor ability and ligand field strength. Ligand field changes associated with photoisomerizable ligands allow tuning of excited-state and ground-state energies that dictate energy/electron transfer, optical/electrical properties, and spin states of a metal center upon photoisomerization, positioning photochromic ligand-metal complexes as promising targets for smart materials.

  4. Pure electronic metal-insulator transition at the interface of complex oxides

    DOE PAGES

    Meyers, D.; Liu, Jian; Freeland, J. W.; ...

    2016-06-21

    We observed complex materials in electronic phases and transitions between them often involve coupling between many degrees of freedom whose entanglement convolutes understanding of the instigating mechanism. Metal-insulator transitions are one such problem where coupling to the structural, orbital, charge, and magnetic order parameters frequently obscures the underlying physics. We demonstrate a way to unravel this conundrum by heterostructuring a prototypical multi-ordered complex oxide NdNiO3 in ultra thin geometry, which preserves the metal-to-insulator transition and bulk-like magnetic order parameter, but entirely suppresses the symmetry lowering and long-range charge order parameter. Furthermore, these findings illustrate the utility of heterointerfaces as amore » powerful method for removing competing order parameters to gain greater insight into the nature of the transition, here revealing that the magnetic order generates the transition independently, leading to an exceptionally rare purely electronic metal-insulator transition with no symmetry change.« less

  5. Synthesis, characterization and spectroscopic properties of the hydrazodye and new hydrazodye-metal complexes

    NASA Astrophysics Data System (ADS)

    Bouhdada, M.; EL Amane, M.

    2017-12-01

    The hydrazodye (L) [disodium (7-hydroxyl-8-phenylazo-1,3-naphthalenedisulfonate)] is prepared and characterized by infrared 1H,13C, NMR and UV-visible spectra. The spectral data of the ligand (L) existing predominantly in the hydrazones form. Reaction of the hydrazodye (L) with Cd2+, Ni2+, Cu2+ and Zn2+ chloride gave two series of metal complexes with general formula [ML2 (OH2)2]2Cl and [ML2 (caf)2]2Cl. Their complexes were identified by FTIR, UV-visible spectra, 1H, 13C, NMR, EPR, XRD and molar conductance. The molar conductance reveals that the new series of metal complexes are non-electrolytes. The postulated octahedral structure of the obtained complexes is also proposed on spectroscopic data analysis.

  6. 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.

  7. Investigation of the Formability of TRIP780 Steel Sheets

    NASA Astrophysics Data System (ADS)

    Song, Yang

    The formability of a metal sheet is dependent on its work hardening behaviour and its forming limits; and both aspects must be carefully determined in order to accurately simulate a particular forming process. This research aims to characterize the formability of a TRIP780 sheet steel using advanced experimental testing and analysis techniques. A series of flat rolling and tensile tests, as well as shear tests were conducted to determine the large deformation work hardening behaviour of this TRIP780 steel. Nakazima tests were carried out up to fracture to determine the forming limits of this sheet material. A highly-automated method for generating a robust FLC for sheet materials from DIC strain measurements was created with the help of finite element simulations, and evaluated against the conventional method. A correction algorithm that aims to compensate for the process dependent effects in the Nakazima test was implemented and tested with some success.

  8. Mixed-valent dicobalt and iron-cobalt complexes with high-spin configurations and short metal-metal bonds.

    PubMed

    Zall, Christopher M; Clouston, Laura J; Young, Victor G; Ding, Keying; Kim, Hyun Jung; Zherebetskyy, Danylo; Chen, Yu-Sheng; Bill, Eckhard; Gagliardi, Laura; Lu, Connie C

    2013-08-19

    Cobalt-cobalt and iron-cobalt bonds are investigated in coordination complexes with formally mixed-valent [M2](3+) cores. The trigonal dicobalt tris(diphenylformamidinate) compound, Co2(DPhF)3, which was previously reported by Cotton, Murillo, and co-workers (Inorg. Chim. Acta 1996, 249, 9), is shown to have an energetically isolated, high-spin sextet ground-state by magnetic susceptibility and electron paramagnetic resonance (EPR) spectroscopy. A new tris(amidinato)amine ligand platform is introduced. By tethering three amidinate donors to an apical amine, this platform offers two distinct metal-binding sites. Using the phenyl-substituted variant (abbreviated as L(Ph)), the isolation of a dicobalt homobimetallic and an iron-cobalt heterobimetallic are demonstrated. The new [Co2](3+) and [FeCo](3+) cores have high-spin sextet and septet ground states, respectively. Their solid-state structures reveal short metal-metal bond distances of 2.29 Å for Co-Co and 2.18 Å for Fe-Co; the latter is the shortest distance for an iron-cobalt bond to date. To assign the positions of iron and cobalt atoms as well as to determine if Fe/Co mixing is occurring, X-ray anomalous scattering experiments were performed, spanning the Fe and Co absorption energies. These studies show only a minor amount of metal-site mixing in this complex, and that FeCoL(Ph) is more precisely described as (Fe0.94(1)Co0.06(1))(Co0.95(1)Fe0.05(1))L(Ph). The iron-cobalt heterobimetallic has been further characterized by Mössbauer spectroscopy. Its isomer shift of 0.65 mm/s and quadrupole splitting of 0.64 mm/s are comparable to the related diiron complex, Fe2(DPhF)3. On the basis of spectroscopic data and theoretical calculations, it is proposed that the formal [M2](3+) cores are fully delocalized.

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

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

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

  10. 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.

  11. Modeling the fracture of ice sheets on parallel computers.

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Waisman, Haim; Bell, Robin; Keyes, David

    2010-03-01

    The objective of this project is to investigate the complex fracture of ice and understand its role within larger ice sheet simulations and global climate change. At the present time, ice fracture is not explicitly considered within ice sheet models due in part to large computational costs associated with the accurate modeling of this complex phenomena. However, fracture not only plays an extremely important role in regional behavior but also influences ice dynamics over much larger zones in ways that are currently not well understood. Dramatic illustrations of fracture-induced phenomena most notably include the recent collapse of ice shelves inmore » Antarctica (e.g. partial collapse of the Wilkins shelf in March of 2008 and the diminishing extent of the Larsen B shelf from 1998 to 2002). Other fracture examples include ice calving (fracture of icebergs) which is presently approximated in simplistic ways within ice sheet models, and the draining of supraglacial lakes through a complex network of cracks, a so called ice sheet plumbing system, that is believed to cause accelerated ice sheet flows due essentially to lubrication of the contact surface with the ground. These dramatic changes are emblematic of the ongoing change in the Earth's polar regions and highlight the important role of fracturing ice. To model ice fracture, a simulation capability will be designed centered around extended finite elements and solved by specialized multigrid methods on parallel computers. In addition, appropriate dynamic load balancing techniques will be employed to ensure an approximate equal amount of work for each processor.« less

  12. High surface area graphene-supported metal chalcogenide assembly

    DOEpatents

    Worsley, Marcus A.; Kuntz, Joshua D.; Orme, Christine A.

    2017-04-25

    Disclosed here is a method for hydrocarbon conversion, comprising contacting at least one graphene-supported assembly with at least one hydrocarbon feedstock, wherein the graphene-supported assembly comprises (i) a three-dimensional network of graphene sheets crosslinked by covalent carbon bonds and (ii) at least one metal chalcogenide compound disposed on the graphene sheets, wherein the chalcogen of the metal chalcogenide compound is selected from S, Se and Te, and wherein the metal chalcogenide compound accounts for at least 20 wt. % of the graphene-supported assembly.

  13. Metal Fabricating Specialist (AFSC 55252).

    ERIC Educational Resources Information Center

    Air Univ., Gunter AFS, Ala. Extension Course Inst.

    This seven-volume student text is designed for use by Air Force personnel enrolled in a self-study extension course for metal fabricating specialists. Covered in the individual volumes are general subjects (career progression, management of activities and resources, shop mathematics, and characteristics of metals); sheet metal tools and equipment…

  14. Asymmetric Catalysis with bis(hydroxyphenyl)diamides/rare-earth metal complexes.

    PubMed

    Kumagai, Naoya; Shibasaki, Masakatsu

    2013-01-02

    A series of asymmetric catalysts composed of conformationally flexible amide-based chiral ligands and rare-earth metals was developed for proton-transfer catalysis. These ligands derived from amino acids provide an intriguing chiral platform for the formation of asymmetric catalysts upon complexation with rare-earth metals. The scope of this arsenal of catalysts was further broadened by the development of heterobimetallic catalytic systems. The cooperative function of hydrogen bonding and metal coordination resulted in intriguing substrate specificity and stereocontrol, and the dynamic nature of the catalysts led to a switch of their function. Herein, we summarize our recent exploration of this class of catalysts. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Forced tearing of ductile and brittle thin sheets.

    PubMed

    Tallinen, T; Mahadevan, L

    2011-12-09

    Tearing a thin sheet by forcing a rigid object through it leads to complex crack morphologies; a single oscillatory crack arises when a tool is driven laterally through a brittle sheet, while two diverging cracks and a series of concertinalike folds forms when a tool is forced laterally through a ductile sheet. On the other hand, forcing an object perpendicularly through the sheet leads to radial petallike tears in both ductile and brittle materials. To understand these different regimes we use a combination of experiments, simulations, and simple theories. In particular, we describe the transition from brittle oscillatory tearing via a single crack to ductile concertina tearing with two tears by deriving laws that describe the crack paths and wavelength of the concertina folds and provide a simple phase diagram for the morphologies in terms of the material properties of the sheet and the relative size of the tool.

  16. Characterization of Platinum Nanoparticles Deposited on Functionalized Graphene Sheets

    PubMed Central

    Chiang, Yu-Chun; Liang, Chia-Chun; Chung, Chun-Ping

    2015-01-01

    Due to its special electronic and ballistic transport properties, graphene has attracted much interest from researchers. In this study, platinum (Pt) nanoparticles were deposited on oxidized graphene sheets (cG). The graphene sheets were applied to overcome the corrosion problems of carbon black at operating conditions of proton exchange membrane fuel cells. To enhance the interfacial interactions between the graphene sheets and the Pt nanoparticles, the oxygen-containing functional groups were introduced onto the surface of graphene sheets. The results showed the Pt nanoparticles were uniformly dispersed on the surface of graphene sheets with a mean Pt particle size of 2.08 nm. The Pt nanoparticles deposited on graphene sheets exhibited better crystallinity and higher oxygen resistance. The metal Pt was the predominant Pt chemical state on Pt/cG (60.4%). The results from the cyclic voltammetry analysis showed the value of the electrochemical surface area (ECSA) was 88 m2/g (Pt/cG), much higher than that of Pt/C (46 m2/g). The long-term test illustrated the degradation in ECSA exhibited the order of Pt/C (33%) > Pt/cG (7%). The values of the utilization efficiency were calculated to be 64% for Pt/cG and 32% for Pt/C. PMID:28793577

  17. Rhodamine spirolactam sensors operated by sulfur-cooperated metal complexation

    NASA Astrophysics Data System (ADS)

    Heo, Gisuk; Lee, Dahye; Kim, Chi Gwan; Do, Jung Yun

    2018-01-01

    New rhodamine Schiff base sensors were developed to improve selective sensing by introducing sulfide, ester, and dithiocarbonate groups, as well as using ketones coupled to rhodamine-hydrazine. Metal sensing proceeded through the 1:1 complexation of the metal ion for most sensors in the presence of Cu2 + and Hg2 +. A sensor carrying a dithiocarbonate group responded selectively to Hg2 + showing a strong colorimetric change and intense fluorescence. The association constants of the sensors were determined from a linear plot performed at micro-molar concentrations to afford values in the range of 104. Sensing was interrupted at the initial time of Hg2 + exposure due to the isomerization of imine and preferential metal bonding of two dithiocarbonate groups regardless of the main structure of rhodamine. The sensors exhibited the reversible and reproducible performance for Hg2 + sensing.

  18. Four transition metal complexes with a semicarbazone ligand bearing pyrazine unit

    NASA Astrophysics Data System (ADS)

    Chen, Hong; Ma, Xiu-qin; Lv, Yan-yun; Jia, Lei; Xu, Jun; Wang, Yuan; Ge, Zhi-jun

    2016-04-01

    Four new complexes based on L (where L = 3-ethyl-2-acetylpyrazine semicarbazone), namely [CoL2]Cl2·0.5H2O (1), [CoL2](NO3)2 (2), [CdL(H2O)2(NO3)](NO3)·H2O (3) and [CuL(CH3OH)Cl2]·[CuLCl2] (4) have been synthesized and characterized by X-ray diffraction analyses. The results show that the semicarbazone acts as a tridentate neutral ligand in all complexes. Each of complex 1 and 2 reveals a distorted octahedral geometry around the metal ion provided by two units of the ligand, while the ratio of the ligand and metal is 1:1 in complexes 3 and 4. The effect of complexes 1-4 on cell proliferation, apoptosis of human pancreatic cancer (Patu8988), human gastric cancer (SGC7901) and human hepatic cancer (SMMC7721) cell lines have been detected by MTT assay, Annexin V/PI double staining flow cytometry and TUNEL assay. The results show that complexes 1-4 can inhibit cell proliferation of Patu8988, SGC7901 and SMMC7721 cells, significantly higher than the effect of the ligand. However, the complex 4 reveals higher apoptosis rate, and displays up-regulated expression level of caspase 3, detected by western blotting, which also indicates the complex 4 can induce caspase-dependent cell apoptosis in SMMC7721.

  19. Supramolecular assembly of group 11 phosphorescent metal complexes for chemosensors of alcohol derivatives

    NASA Astrophysics Data System (ADS)

    Lintang, H. O.; Ghazalli, N. F.; Yuliati, L.

    2018-04-01

    We report on systematic study on vapochromic sensing of ethanol by using phosphorescent trinuclear metal pyrazolate complexes with supramolecular assembly of weak intermolecular metal-metal interactions using 4-(3,5-dimethoxybenzyl)-3,5-dimethyl pyrazole ligand (1) and group 11 metal ions (Cu(I), Ag(I), Au(I)). Upon excitation at 284, the resulting complexes showed emission bands with a peak centered at 616, 473 and 612 nm for 2(Cu), 2(Ag) and 2(Au), respectively. Chemosensor 2(Cu) showed positive response to ethanol vapors in 5 mins by blue-shifting its emission band from 616 to 555 nm and emitting bright orange to green. Otherwise 2(Au) gave shifting from its emission band centered at 612 to 587 nm with Δλ of 25 nm (41%) and color changes from red-orange to light green-orange while 2(Ag) showed quenching in its original emission intensity at 473 nm in 40% with color changes from dark green to less emissive. These results demonstrate that sensing capability of chemosensor 2(Cu) with suitable molecular design of ligand and metal ion in the complex is due to the formation of a weak intermolecular hydrogen bonding interaction of O atom at the methoxy of the benzyl ring with the OH of the vapors at the outside of the molecules.

  20. Radical bonding: structure and stability of bis(phenalenyl) complexes of divalent metals from across the periodic table.

    PubMed

    Craciun, Smaranda; Donald, Kelling J

    2009-07-06

    We examine the bonding possibilities of the bis(phenalenyl) MP(2) sandwich complexes of the divalent metals M = Be, Mg, Ca, Sr, Ba, Zn, Cd, and Hg, at the B3LYP level of theory. The outcome is an extraordinarily diverse class of low symmetry bis(phenalenyl)metal complexes in which bonding preferences and binding enthalpies differ dramatically. The lowest energy group 2 metal MP(2) complexes include an intriguing eta(1),eta(3) BeP(2) structure, and bent eta(6),eta(6) systems for M = Ca, Sr, and Ba. The group 12 bis(phenalenyl) complexes are thermodynamically unstable eta(1),eta(1) slip-sandwich structures. To better understand changes in the structural preferences going from the (eta(6),eta(6)) group 2 to the (eta(1),eta(1)) group 12 complexes, we explored the bonding in the bis(phenalenyl) complexes of transition metals with stable +2 oxidations states between Ca and Zn in period 4. The computed binding enthalpies are large and negative for nearly all of the minimum energy bis(phenalenyl) complexes of the group 2 and the transition metals; they are tiny for MgP(2), and are quite positive for the group 12 systems. The structural preferences and stability of the complexes is a subtle negotiation of several influences: the (un)availability of (n - 1)d and np, orbitals for bonding, the cost of the rehybridization at carbon sites in the phenalenyl rings in preparation for bonding to the metals, and the (P---P) interaction between the phenalenyl radicals.

  1. Spectro Analytical, Computational and In Vitro Biological Studies of Novel Substituted Quinolone Hydrazone and it's Metal Complexes.

    PubMed

    Nagula, Narsimha; Kunche, Sudeepa; Jaheer, Mohmed; Mudavath, Ravi; Sivan, Sreekanth; Ch, Sarala Devi

    2018-01-01

    Some novel transition metal [Cu (II), Ni (II) and Co (II)] complexes of nalidixic acid hydrazone have been prepared and characterized by employing spectro-analytical techniques viz: elemental analysis, 1 H-NMR, Mass, UV-Vis, IR, TGA-DTA, SEM-EDX, ESR and Spectrophotometry studies. The HyperChem 7.5 software was used for geometry optimization of title compound in its molecular and ionic forms. Quantum mechanical parameters, contour maps of highest occupied molecular orbitals (HOMO) and lowest unoccupied molecular orbitals (LUMO) and corresponding binding energy values were computed using semi empirical single point PM3 method. The stoichiometric equilibrium studies of metal complexes carried out spectrophotometrically using Job's continuous variation and mole ratio methods inferred formation of 1:2 (ML 2 ) metal complexes in respective systems. The title compound and its metal complexes screened for antibacterial and antifungal properties, exemplified improved activity in metal complexes. The studies of nuclease activity for the cleavage of CT- DNA and MTT assay for in vitro cytotoxic properties involving metal complexes exhibited high activity. In addition, the DNA binding properties of Cu (II), Ni (II) and Co (II) complexes investigated by electronic absorption and fluorescence measurements revealed their good binding ability and commended agreement of K b values obtained from both the techniques. Molecular docking studies were also performed to find the binding affinity of synthesized compounds with DNA (PDB ID: 1N37) and "Thymidine phosphorylase from E.coli" (PDB ID: 4EAF) protein targets.

  2. Bimetallic d10 -Metal Complexes of a Bipyridine Substituted N-Heterocyclic Carbene.

    PubMed

    Kaub, Christoph; Lebedkin, Sergei; Li, Alina; Kruppa, Sebastian V; Strebert, Patrick H; Kappes, Manfred M; Riehn, Christoph; Roesky, Peter W

    2018-04-20

    The hybrid ligand 3-(2,2'-bipyridine-6-ylmethyl)-1-mesityl-1H-imidazolylidene (NHC Bipy ) featuring both carbene and N-donor sites, was selectively complexed with various d 10 metal cations in order to examine its coordination behavior with regard to homo and heterometallic structures. Respective silver complexes can be obtained by the silver oxide route and are suitable transmetallation reagents for the synthesis of gold(I) compounds. Starting from the mononuclear complexes [(NHC Bipy )AuCl], [(NHC Bipy )Au(C 6 F 5 )] and [(NHC Bipy ) 2 Au][ClO 4 ], open-chain as well as cyclic heterobimetallic complexes containing Cu + , Ag + , Zn 2+ , Cd 2+ , and Hg 2+ were synthesized. Furthermore, the homobimetallic species [(NHC Bipy ) 2 M 2 ][ClO 4 ] 2 (M=Cu, Ag) were obtained. All bimetallic compounds were fully characterized including single-crystal X-ray analysis. Their photoluminescence (PL) properties were investigated in the solid state at temperatures between 15 and 295 K and compared with those of the mononuclear species. There is a clear difference in PL properties between the open chain and the cyclic heterobimetallic complexes. The latter species show different PL properties, depending on the metals involved. In addition, collision-induced dissociation (CID) experiments were performed on electrosprayed cations of the cyclic heterobimetallic compounds, to compare the metal binding at the carbene and N-donor sites. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Metal Complexation in Xylem Fluid 1

    PubMed Central

    White, Michael C.; Decker, A. Morris; Chaney, Rufus L.

    1981-01-01

    Xylem fluid was analyzed for numerous solutes to characterize chemically the sap as a medium for forming and transporting metal complexes. The stem exudate was collected hourly for 8 hours from topped 31-day-old soybean (Glycine max L. Merr.) and 46-day-old tomato (Lycopersicon esculentum Mill.) plants grown in normal (0.5 micromolar) and Za-phytotoxic nutrient solutions. Soybean plants were grown in the normal and high-Zn solutions for 24 days; tomato plants were grown for 32 days. The exudate was analyzed for seven organic acids, 22 amino acids, eight inorganic solutes, apparent ionic strength, and pH. Significant changes in many solutes occurred over the 8-hour sampling period. These fluctuations depended on plant species, individual solute, and Zn treatment, and demonstrated that extrapolation of xylem-fluid analyses to whole-plant xylem sap is valid only for sap samples collected shortly after topping a plant. Exudate pH decreased over the 8-hour period for both species; exudate ionic strength increased for tomato and decreased for soybean. At the normal-Zn treatment (0 to 1 hour), the highest acid micromolar concentrations in soybean exudate were: asparagine, 2,583; citric, 1,706; malic, 890; and malonic, 264. Under the same conditions, the highest acid micromolar concentrations in tomato exudate were: maleic, 1,206; malic, 628; glutamine, 522; citric, 301; and asparagine, 242. Cysteine and methionine were above detection limits only in soybean exudate. Zinc phytotoxicity caused significant changes in many solutes. The analyses reported here provide a comprehensive data base for further studies on metal-complex equilibria in xylem fluid. PMID:16661664

  4. Formation of metal-nicotianamine complexes as affected by pH, ligand exchange with citrate and metal exchange. A study by electrospray ionization time-of-flight mass spectrometry.

    PubMed

    Rellán-Alvarez, Rubén; Abadía, Javier; Alvarez-Fernández, Ana

    2008-05-01

    Nicotianamine (NA) is considered as a key element in plant metal homeostasis. This non-proteinogenic amino acid has an optimal structure for chelation of metal ions, with six functional groups that allow octahedral coordination. The ability to chelate metals by NA is largely dependent on the pK of the resulting complex and the pH of the solution, with most metals being chelated at neutral or basic pH values. In silico calculations using pKa and pK values have predicted the occurrence of metal-NA complexes in plant fluids, but the use of soft ionization techniques (e.g. electrospray), together with high-resolution mass spectrometers (e.g. time-of-flight mass detector), can offer direct and metal-specific information on the speciation of NA in solution. We have used direct infusion electrospray ionization mass spectrometry (time-of-flight) ESI-MS(TOF) to study the complexation of Mn, Fe(II), Fe(III), Ni, Cu by NA. The pH dependence of the metal-NA complexes in ESI-MS was compared to that predicted in silico. Possible exchange reactions that may occur between Fe-NA and other metal micronutrients as Zn and Cu, as well as between Fe-NA and citrate, another possible Fe ligand candidate in plants, were studied at pH 5.5 and 7.5, values typical of the plant xylem and phloem saps. Metal-NA complexes were generally observed in the ESI-MS experiments at a pH value approximately 1-2 units lower than that predicted in silico, and this difference could be only partially explained by the estimated error, approximately 0.3 pH units, associated with measuring pH in organic solvent-containing solutions. Iron-NA complexes are less likely to participate in ligand- and metal-exchange reactions at pH 7.5 than at pH 5.5. Results support that NA may be the ligand chelating Fe at pH values usually found in phloem sap, whereas in the xylem sap NA is not likely to be involved in Fe transport, conversely to what occurs with other metals such as Cu and Ni. Some considerations that need to be

  5. Experimental investigation of a 1 kA/cm{sup 2} sheet beam plasma cathode electron gun

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kumar, Niraj, E-mail: niraj.ceeri@gmail.com; Narayan Pal, Udit; Prajesh, Rahul

    In this paper, a cold cathode based sheet-beam plasma cathode electron gun is reported with achieved sheet-beam current density ∼1 kA/cm{sup 2} from pseudospark based argon plasma for pulse length of ∼200 ns in a single shot experiment. For the qualitative assessment of the sheet-beam, an arrangement of three isolated metallic-sheets is proposed. The actual shape and size of the sheet-electron-beam are obtained through a non-conventional method by proposing a dielectric charging technique and scanning electron microscope based imaging. As distinct from the earlier developed sheet beam sources, the generated sheet-beam has been propagated more than 190 mm distance inmore » a drift space region maintaining sheet structure without assistance of any external magnetic field.« less

  6. Sulphide mineral evolution and metal mobility during alteration of the oceanic crust: Insights from ODP Hole 1256D

    NASA Astrophysics Data System (ADS)

    Patten, C. G. C.; Pitcairn, I. K.; Teagle, D. A. H.; Harris, M.

    2016-11-01

    Fluxes of metals during the hydrothermal alteration of the oceanic crust have far reaching effects including buffering of the compositions of the ocean and lithosphere, supporting microbial life and the formation of sulphide ore deposits. The mechanisms responsible for metal mobilisation during the evolution of the oceanic crust are complex and are neither fully constrained nor quantified. Investigations into the mineral reactions that release metals, such as sulphide leaching, would generate better understanding of the controls on metal mobility in the oceanic crust. We investigate the sulphide and oxide mineral paragenesis and the extent to which these minerals control the metal budget in samples from Ocean Drilling Program (ODP) Hole 1256D. The ODP Hole 1256D drill core provides a unique sample suite representative of a complete section of a fast-spreading oceanic crust from the volcanic section down to the plutonic complex. The sulphide population at Hole 1256D is divided into five groups based on mineralogical assemblage, lithological location and texture: the magmatic, metasomatised, high temperature hydrothermal, low temperature and patchy sulphides. The initiation of hydrothermal alteration by downward flow of moderate temperature (250-350 °C) hydrothermal fluids under oxidising conditions leads to metasomatism of the magmatic sulphides in the sheeted dyke and plutonic complexes. Subsequent increase in the degree of hydrothermal alteration at temperatures >350 °C under reducing conditions then leads to the leaching of the metasomatised sulphides by rising hydrothermal fluids. Mass balance calculations show that the mobility of Cu, Se and Au occurs through sulphide leaching during high temperature hydrothermal alteration and that the mobility of Zn, As, Sb and Pb is controlled by silicate rather than sulphide alteration. Sulphide leaching is not complete at Hole 1256D and more advanced alteration would mobilise greater masses of metals. Alteration of oxide

  7. Key technologies for manufacturing and processing sheet materials: A global perspective

    NASA Astrophysics Data System (ADS)

    Demeri, Mahmoud Y.

    2001-02-01

    Modern industrial technologies continue to seek new materials and processes to produce products that meet design and functional requirements. Sheet materials made from ferrous and non-ferrous metals, laminates, composites, and reinforced plastics constitute a large percentage of today’s products, components, and systems. Major manufacturers of sheet products include automotive, aerospace, appliance, and food-packaging industries. The Second Global Symposium on Innovations in Materials Processing & Manufacturing: Sheet Materials is organized to provide a forum for presenting advances in sheet processing and manufacturing by worldwide researchers and engineers from industrial, research, and academic centers. The symposium, sponsored by the TMS Materials Processing & Manufacturing Division (MPMD), was planned for the 2001 TMS Annual Meeting, New Orleans, Louisiana, February 11 15, 2001. This article is a review of key papers submitted for publication in the concurrent volume. The selected papers present significant developments in the rapidly expanding areas of advanced sheet materials, innovative forming methods, industrial applications, primary and secondary processing, composite processing, and numerical modeling of manufacturing processes.

  8. Room temperature mechanical properties of electron beam welded zircaloy-4 sheet

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Parga, C. J.; Rooyen, I. J.; Coryell, B. D.

    Room temperature mechanical properties of electron beam welded and plain Zircaloy-4 sheet (1.6mm thick) have been measured and compared. Various welding parameters were utilized to join sheet material. Electron beam welded specimens and as-received sheet specimens show comparable mechanical properties. Zr-4 sheet displays anisotropy; tensile properties measured for transverse display higher elastic modulus, yield strength, reduction of area and slightly lower ductility than for the longitudinal (rolling direction). Higher welding power increases the alloy’s hardness, elastic modulus and yield strength, with a corresponding decrease in tensile strength and ductility. The hardness measured at weld is comparable to the parent metalmore » hardness. Hardness at heat-affected-zone is slightly higher. Electron microscopic examination shows distinct microstructure morphology and grain size at the weld zone, HAZ and parent metal. A correlation between welding parameters, mechanical properties and microstructural features was established for electron beam welded Zircaloy-4 sheet material.« less

  9. Room temperature mechanical properties of electron beam welded zircaloy-4 sheet

    DOE PAGES

    Parga, C. J.; Rooyen, I. J.; Coryell, B. D.; ...

    2017-11-04

    Room temperature mechanical properties of electron beam welded and plain Zircaloy-4 sheet (1.6mm thick) have been measured and compared. Various welding parameters were utilized to join sheet material. Electron beam welded specimens and as-received sheet specimens show comparable mechanical properties. Zr-4 sheet displays anisotropy; tensile properties measured for transverse display higher elastic modulus, yield strength, reduction of area and slightly lower ductility than for the longitudinal (rolling direction). Higher welding power increases the alloy’s hardness, elastic modulus and yield strength, with a corresponding decrease in tensile strength and ductility. The hardness measured at weld is comparable to the parent metalmore » hardness. Hardness at heat-affected-zone is slightly higher. Electron microscopic examination shows distinct microstructure morphology and grain size at the weld zone, HAZ and parent metal. A correlation between welding parameters, mechanical properties and microstructural features was established for electron beam welded Zircaloy-4 sheet material.« less

  10. Influence of nanotopography on periodontal ligament stem cell functions and cell sheet based periodontal regeneration

    PubMed Central

    Gao, Hui; Li, Bei; Zhao, Lingzhou; Jin, Yan

    2015-01-01

    Periodontal regeneration is an important part of regenerative medicine, with great clinical significance; however, the effects of nanotopography on the functions of periodontal ligament (PDL) stem cells (PDLSCs) and on PDLSC sheet based periodontal regeneration have never been explored. Titania nanotubes (NTs) layered on titanium (Ti) provide a good platform to study this. In the current study, the influence of NTs of different tube size on the functions of PDLSCs was observed. Afterward, an ectopic implantation model using a Ti/cell sheets/hydroxyapatite (HA) complex was applied to study the effect of the NTs on cell sheet based periodontal regeneration. The NTs were able to enhance the initial PDLSC adhesion and spread, as well as collagen secretion. With the Ti/cell sheets/HA complex model, it was demonstrated that the PDLSC sheets were capable of regenerating the PDL tissue, when combined with bone marrow mesenchymal stem cell (BMSC) sheets and HA, without the need for extra soluble chemical cues. Simultaneously, the NTs improved the periodontal regeneration result of the ectopically implanted Ti/cell sheets/HA complex, giving rise to functionally aligned collagen fiber bundles. Specifically, much denser collagen fibers, with abundant blood vessels as well as cementum-like tissue on the Ti surface, which well-resembled the structure of natural PDL, were observed in the NT5 and NT10 sample groups. Our study provides the first evidence that the nanotopographical cues obviously influence the functions of PDLSCs and improve the PDLSC sheet based periodontal regeneration size dependently, which provides new insight to the periodontal regeneration. The Ti/cell sheets/HA complex may constitute a good model to predict the effect of biomaterials on periodontal regeneration. PMID:26150714

  11. Influence of nanotopography on periodontal ligament stem cell functions and cell sheet based periodontal regeneration.

    PubMed

    Gao, Hui; Li, Bei; Zhao, Lingzhou; Jin, Yan

    2015-01-01

    Periodontal regeneration is an important part of regenerative medicine, with great clinical significance; however, the effects of nanotopography on the functions of periodontal ligament (PDL) stem cells (PDLSCs) and on PDLSC sheet based periodontal regeneration have never been explored. Titania nanotubes (NTs) layered on titanium (Ti) provide a good platform to study this. In the current study, the influence of NTs of different tube size on the functions of PDLSCs was observed. Afterward, an ectopic implantation model using a Ti/cell sheets/hydroxyapatite (HA) complex was applied to study the effect of the NTs on cell sheet based periodontal regeneration. The NTs were able to enhance the initial PDLSC adhesion and spread, as well as collagen secretion. With the Ti/cell sheets/HA complex model, it was demonstrated that the PDLSC sheets were capable of regenerating the PDL tissue, when combined with bone marrow mesenchymal stem cell (BMSC) sheets and HA, without the need for extra soluble chemical cues. Simultaneously, the NTs improved the periodontal regeneration result of the ectopically implanted Ti/cell sheets/HA complex, giving rise to functionally aligned collagen fiber bundles. Specifically, much denser collagen fibers, with abundant blood vessels as well as cementum-like tissue on the Ti surface, which well-resembled the structure of natural PDL, were observed in the NT5 and NT10 sample groups. Our study provides the first evidence that the nanotopographical cues obviously influence the functions of PDLSCs and improve the PDLSC sheet based periodontal regeneration size dependently, which provides new insight to the periodontal regeneration. The Ti/cell sheets/HA complex may constitute a good model to predict the effect of biomaterials on periodontal regeneration.

  12. The influence of heat treatment on properties of cold rolled alloyed steel and nickel superalloys sheets used in aircraft industry

    NASA Astrophysics Data System (ADS)

    Zaba, K.; Dul, I.; Puchlerska, S.

    2017-02-01

    Superalloys based on nickel and selected steels are widely used in the aerospace industry, because of their excellent mechanical properties, heat resistance and creep resistance. Metal sheets of these materials are plastically deformed and applied, inter alia, to critical components of aircraft engines. Due to their chemical composition these materials are hardly deformable. There are various methods to improve the formability of these materials, including plastic deformation at an elevated or high temperature, or a suitable heat treatment before forming process. The paper presents results of the metal sheets testing after heat treatment. For the research, sheets of two types of nickel superalloys type Inconel and of three types of steel were chosen. The materials were subjected to multivariate heat treatment at different temperature range and time. After this step, mechanical properties were examined according to the metal sheet rolling direction. The results were compared and the optimal type of pre-trial softening heat treatment for each of the materials was determined.

  13. On the existence of free and metal complexed sulfide in the Arabian Sea and its oxygen minimum zone

    NASA Astrophysics Data System (ADS)

    Theberge, Stephen M.; Luther, George W.; Farrenkopf, Anna M.

    Free hydrogen sulfide was not detected in the oxygen minimum zone (OMZ) of the Arabian Sea during legs D1 (September 1992) and D3 (October-November 1992) of the Netherlands Indian Ocean Programme (NIOP). However, sulfide complexed to metals was detected by cathodic stripping square wave voltammetry at 2 nM or less throughout the water column. A slight increase in sulfide was measured in the OMZ relative to the surface waters and may be related to sulfur release from organic matter during decomposition. Sulfide complexes are of two general types at low concentrations of metal and sulfide. First, metals such as Mn, Fe, Co and Ni form complexes with bisulfide ion (HS -) that are kinetically labile to dissociation and are reactive. Second, metals such as Cu and Zn form multinuclear complexes with sulfide (S 2-) that are kinetically inert to dissociation; thus, they are less reactive than free (bi)sulfide and the labile metal bisulfide complexes. Zinc and copper sulfide complexes are important in allowing hydrogen sulfide to persist in seawater which contains measurable oxygen.

  14. Synthesis, Characterization and Biological Evaluation of Transition Metal Complexes Derived from N, S Bidentate Ligands

    PubMed Central

    Md Yusof, Enis Nadia; Ravoof, Thahira Begum S. A.; Tiekink, Edward R. T.; Veerakumarasivam, Abhimanyu; Crouse, Karen Anne; Mohamed Tahir, Mohamed Ibrahim; Ahmad, Haslina

    2015-01-01

    Two bidentate NS ligands were synthesized by the condensation reaction of S-2-methylbenzyldithiocarbazate (S2MBDTC) with 2-methoxybenzaldehyde (2MB) and 3-methoxybenzaldehyde (3MB). The ligands were reacted separately with acetates of Cu(II), Ni(II) and Zn(II) yielding 1:2 (metal:ligand) complexes. The metal complexes formed were expected to have a general formula of [M(NS)2] where M = Cu2+, Ni2+, and Zn2+. These compounds were characterized by elemental analysis, molar conductivity, magnetic susceptibility and various spectroscopic techniques. The magnetic susceptibility measurements and spectral results supported the predicted coordination geometry in which the Schiff bases behaved as bidentate NS donor ligands coordinating via the azomethine nitrogen and thiolate sulfur. The molecular structures of the isomeric S2M2MBH (1) and S2M3MBH (2) were established by X-ray crystallography to have very similar l-shaped structures. The Schiff bases and their metal complexes were evaluated for their biological activities against estrogen receptor-positive (MCF-7) and estrogen receptor-negative (MDA-MB-231) breast cancer cell lines. Only the Cu(II) complexes showed marked cytotoxicity against the cancer cell lines. Both Schiff bases and other metal complexes were found to be inactive. In concordance with the cytotoxicity studies, the DNA binding studies indicated that Cu(II) complexes have a strong DNA binding affinity. PMID:25988384

  15. Spectroscopic characterization of metal complexes of novel Schiff base. Synthesis, thermal and biological activity studies

    NASA Astrophysics Data System (ADS)

    Omar, M. M.; Mohamed, Gehad G.; Ibrahim, Amr A.

    2009-07-01

    Novel Schiff base (HL) ligand is prepared via condensation of 4-aminoantipyrine and 2-aminobenzoic acid. The ligand is characterized based on elemental analysis, mass, IR and 1H NMR spectra. Metal complexes are reported and characterized based on elemental analyses, IR, 1H NMR, solid reflectance, magnetic moment, molar conductance and thermal analyses (TGA, DrTGA and DTA). The molar conductance data reveal that all the metal chelates are non-electrolytes. IR spectra show that HL is coordinated to the metal ions in a uninegatively tridentate manner with NNO donor sites of the azomethine N, amino N and deprotonated caroxylic-O. From the magnetic and solid reflectance spectra, it is found that the geometrical structures of these complexes are octahedral. The thermal behaviour of these chelates shows that the hydrated complexes losses water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps. The activation thermodynamic parameters, such as, E*, ΔH*, ΔS* and ΔG* are calculated from the DrTG curves using Coats-Redfern method. The synthesized ligands, in comparison to their metal complexes also were screened for their antibacterial activity against bacterial species, Escherichia Coli, Pseudomonas aeruginosa, Staphylococcus Pyogones and Fungi (Candida). The activity data show that the metal complexes to be more potent/antibacterial than the parent Shciff base ligand against one or more bacterial species.

  16. Electronic structures and magnetic/optical properties of metal phthalocyanine complexes

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Baba, Shintaro; Suzuki, Atsushi, E-mail: suzuki@mat.usp.ac.jp; Oku, Takeo

    2016-02-01

    Electronic structures and magnetic / optical properties of metal phthalocyanine complexes were studied by quantum calculations using density functional theory. Effects of central metal and expansion of π orbital on aromatic ring as conjugation system on the electronic structures, magnetic, optical properties and vibration modes of infrared and Raman spectra of metal phthalocyanines were investigated. Electron and charge density distribution and energy levels near frontier orbital and excited states were influenced by the deformed structures varied with central metal and charge. The magnetic parameters of chemical shifts in {sup 13}C-nuclear magnetic resonance ({sup 13}C-NMR), principle g-tensor, A-tensor, V-tensor of electricmore » field gradient and asymmetry parameters derived from the deformed structures with magnetic interaction of nuclear quadruple interaction based on electron and charge density distribution with a bias of charge near ligand under crystal field.« less

  17. Evidence of an inverted hexagonal phase in self-assembled phospholipid-DNA-metal complexes

    NASA Astrophysics Data System (ADS)

    Francescangeli, O.; Pisani, M.; Stanic, V.; Bruni, P.; Weiss, T. M.

    2004-08-01

    We report the first observation of an inverted hexagonal phase of phospholipid-DNA-metal complexes. These ternary complexes are formed in a self-assembled manner when water solutions of neutral lipid dioleoylphosphatidylethanolamine (DOPE), DNA and divalent metal cations (Me2+; Me=Fe, Co, Mg, Mn) are mixed, which represents a striking example of supramolecular chemistry. The structure, derived from synchrotron X-ray diffraction, consists of cylindrical DNA strands coated by neutral lipid monolayers and arranged on a two-dimensional hexagonal lattice (HIIc). Besides the fundamental aspects, DOPE-DNA-Me2+ complexes may be of great interest as efficient nonviral delivery systems in gene therapy applications because of the low inherent cytotoxicity and the potential high transfection efficiency.

  18. Humic Acid Complexation of Th, Hf and Zr in Ligand Competition Experiments: Metal Loading and Ph Effects

    NASA Technical Reports Server (NTRS)

    Stern, Jennifer C.; Foustoukos, Dionysis I.; Sonke, Jeroen E.; Salters, Vincent J. M.

    2014-01-01

    The mobility of metals in soils and subsurface aquifers is strongly affected by sorption and complexation with dissolved organic matter, oxyhydroxides, clay minerals, and inorganic ligands. Humic substances (HS) are organic macromolecules with functional groups that have a strong affinity for binding metals, such as actinides. Thorium, often studied as an analog for tetravalent actinides, has also been shown to strongly associate with dissolved and colloidal HS in natural waters. The effects of HS on the mobilization dynamics of actinides are of particular interest in risk assessment of nuclear waste repositories. Here, we present conditional equilibrium binding constants (Kc, MHA) of thorium, hafnium, and zirconium-humic acid complexes from ligand competition experiments using capillary electrophoresis coupled with ICP-MS (CE- ICP-MS). Equilibrium dialysis ligand exchange (EDLE) experiments using size exclusion via a 1000 Damembrane were also performed to validate the CE-ICP-MS analysis. Experiments were performed at pH 3.5-7 with solutions containing one tetravalent metal (Th, Hf, or Zr), Elliot soil humic acid (EHA) or Pahokee peat humic acid (PHA), and EDTA. CE-ICP-MS and EDLE experiments yielded nearly identical binding constants for the metal- humic acid complexes, indicating that both methods are appropriate for examining metal speciation at conditions lower than neutral pH. We find that tetravalent metals form strong complexes with humic acids, with Kc, MHA several orders of magnitude above REE-humic complexes. Experiments were conducted at a range of dissolved HA concentrations to examine the effect of [HA]/[Th] molar ratio on Kc, MHA. At low metal loading conditions (i.e. elevated [HA]/[Th] ratios) the ThHA binding constant reached values that were not affected by the relative abundance of humic acid and thorium. The importance of [HA]/[Th] molar ratios on constraining the equilibrium of MHA complexation is apparent when our estimated Kc, MHA values

  19. Surfactant-thermal method to synthesize a new Zn(II)-trimesic MOF with confined Ru(bpy){sub 3}{sup 2+} complex

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Xu, Hui; Gao, Junkuo, E-mail: jkgao@zstu.edu.cn; Wang, Jiangpeng

    2015-03-15

    A surfactant-thermal method was used to prepare a new zinc-1,3,5-benzentricarboxylate-based metal-organic framework (ZJU-100) with confined Ru(bpy){sub 3}{sup 2+} (RuBpy) complex by using surfactant PEG 400 as reaction medium. The RuBpy molecules were encapsulated between the 2-D sheets in ZJU-100. ZJU-100 showed bathochromic shift in the steady-state emission spectrum and increased emission lifetimes relative to RuBpy molecules. The extended lifetime is attributed to the reduced nonradiative decay rate due to the stabilization of RuBpy within the rigid MOF framework. These results represent the first example of MOF with confined complex synthesized by surfactant, indicating that the surfactant-thermal method could offer excitingmore » opportunities for preparing new MOFs host/guest materials with novel structures and interesting luminescent properties. - Graphical abstract: A surfactant-thermal method was used to prepare a new zinc-1,3,5-benzentricarboxylate-based metal-organic framework (ZJU-100) with confined Ru(bpy){sub 3}{sup 2+} (RuBpy) complex by using surfactant PEG 400 as reaction medium. - Highlights: • Surfactant-thermal synthesis of crystalline metal-organic framework host/guest materials. • RuBpy molecules were encapsulated between the 2-D sheets of MOFs. • Extended lifetime is observed due to the stabilization of RuBpy within the rigid MOF framework.« less

  20. Synthesis and CV Studies of Dithiol-terminated Metal Terpyridine Complexes

    NASA Technical Reports Server (NTRS)

    Asano, Sylvia; Fan, Wendy; Ng, Hou-Tee; Han, Jie; Meyyappan, M.

    2003-01-01

    Transition metal coordination complexes possess unique electronic structures that should be a good model for studying electronic transport behavior at a molecular level. The discrete, multiple redox states, low redox potential and the superb ability to establish contact with other molecular and electronic components by coordination chemistry have made this a subject of investigation for their possible application as active electronic components in molecular devices. We present the synthesis and electrochemical characterization of 4'-thioacetylphenyl-2'2:6',2"-terpyridine iron(II) complex and compare it with a model bis-terpyridine iron(II) complex by cyclic voltammetry. With the use of different working electrodes, the behavior of these complexes show different electron transfer rates.

  1. Reversible photochromic system based on rhodamine B salicylaldehyde hydrazone metal complex.

    PubMed

    Li, Kai; Xiang, Yu; Wang, Xiaoyan; Li, Ji; Hu, Rongrong; Tong, Aijun; Tang, Ben Zhong

    2014-01-29

    Photochromic molecules are widely applied in chemistry, physics, biology, and materials science. Although a few photochromic systems have been developed before, their applications are still limited by complicated synthesis, low fatigue resistance, or incomplete light conversion. Rhodamine is a class of dyes with excellent optical properties including long-wavelength absorption, large absorption coefficient, and high photostability in its ring-open form. It is an ideal chromophore for the development of new photochromic systems. However, known photochromic rhodamine derivatives, such as amides, exhibit only millisecond lifetimes in their colored ring-open forms, making their application very limited and difficult. In this work, rhodamine B salicylaldehyde hydrazone metal complex was found to undergo intramolecular ring-open reactions upon UV irradiation, which led to a distinct color and fluorescence change both in solution and in solid matrix. The complex showed good fatigue resistance for the reversible photochromism and long lifetime for the ring-open state. Interestingly, the thermal bleaching rate was tunable by using different metal ions, temperatures, solvents, and chemical substitutions. It was proposed that UV light promoted isomerization of the rhodamine B derivative from enol-form to keto-form, which induced ring-opening of the rhodamine spirolactam in the complex to generate color. The photochromic system was successfully applied for photoprinting and UV strength measurement in the solid state. As compared to other reported photochromic molecules, the system in this study has its advantages of facile synthesis and tunable thermal bleaching rate, and also provides new insights into the development of photochromic materials based on metal complex and spirolactam-containing dyes.

  2. 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;…

  3. Analysis of Metals Concentration in the Soils of SIPCOT Industrial Complex, Cuddalore, Tamil Nadu

    PubMed Central

    Mathivanan, V.; Prabavathi, R.; Prithabai, C.; Selvisabhanayakam

    2010-01-01

    Phytoremediation is a promising area of new research, both for its low cost and great benefit to society in the clean retrieval of contaminated sites. Phytoremediation is the use of living green plants for in situ risk reduction and/or removal of contaminants from contaminated soil, water, sediments, and air. Specially selected or engineered plants are used in the process. The soil samples were taken from Cuddalore Old Town (OT) and the samples from SIPCOT industrial complex, which was the study area and analyzed for various metals concentrations. Fifteen metals have been analyzed by adopting standard procedure. The detection limits of metal concentration are drawn as control. The various (15) metal concentrations in the soil samples were found higher in soil taken from SIPCOT industrial complex, compared with samples taken from Cuddalore OT. In all the observations, it was found that most of the metals like calcium, cadmium, chromium, cobalt, nickel, and zinc showed maximum concentrations, whereas arsenic, antimony, lead, magnesium, sodium have shown minimum concentrations, both when compared with control. From the present study, it was found that the soil collected from SIPCOT complex area were more polluted due to the presence of various industrial effluents, municipal wastes, and sewages when compared with the soil collected from Cuddalore OT. PMID:21170256

  4. Synthesis and spectral studies of heterocyclic azo dye complexes with some transition metals

    NASA Astrophysics Data System (ADS)

    Jarad, A. J.; Majeed, I. Y.; Hussein, A. O.

    2018-05-01

    6-(2-benzathiazolyl azo) -3,5-dimethylphenol was formed by grouping the 2-benzothiazole diazonium chloride with 3,5-dimethylphenol. Azo ligand(L) was resolved on the origin by 1H and 13CNMR, FTIR and UV-Vis spectral analysis. Complexation of tridentate ligand (L) with Co2+, Ni2+, Cu2+ and Zn2+ in aqueous of ethyl alcohol with a 1:2 metal:ligand, and at ideal pH.. The formation of metal chelates are assigned using flame atomic absorption, FTIR and UV-Vis spectral analysis, other than conductivity and magnetic estates. The nature of the metal chelates were carried out by mole ratio and continuous variation mechanism, Beer’s law followed the rate (0.0001 - 3×0.0001 M) concentration. High molar absorptivity for the complex solutions were observed. On the origin data an octahedral geometry were described for the metal chelates. Biological activity of the ready compounds were assayed.

  5. Characteristics of the aluminum alloy sheets for forming and application examples

    NASA Astrophysics Data System (ADS)

    Uema, Naoyuki; Asano, Mineo

    2013-12-01

    In this paper, the characteristics and application examples of aluminum alloy sheets developed for automotive parts by Sumitomo Light Metal are described. For the automotive closure panels (ex., hood, back-door), an Al-Mg-Si alloy sheet having an excellent hemming performance was developed. The cause of the occurrence and the propagation of cracks by bending were considered to be the combined effect of the shear bands formed across several crystal grains and the micro-voids formed around the second phase particles. By reducing the shear band formation during bending by controlling the crystallographic texture, the Al-Mg-Si alloy sheets showed an excellent hemming performance. For the automotive outer panels (ex., roof, fender, trunk-lid), an Al-Mg alloy sheet, which has both a good hot blow formability and excellent surface appearance after hot blow forming was developed, and hot blow forming technology was put to practical use using this developed Al-Mg alloy sheet. For automotive heat insulators, a high ductile Al-Fe alloy sheet was developed. The heat insulator, which integrated several panels, was put into practical use using this developed Al-Fe alloy sheet. The textured sheet was often used as a heat insulator in order to reduce the thickness of the aluminum alloy sheet and obtain good press formability. The new textured sheet, which has both high rigidity and good press formability for heat insulators, was developed by FE analysis.

  6. Structural and Spectral Properties of Curcumin and Metal- Curcumin Complex Derived from Turmeric (Curcuma longa)

    NASA Astrophysics Data System (ADS)

    Bich, Vu Thi; Thuy, Nguyen Thi; Binh, Nguyen Thanh; Huong, Nguyen Thi Mai; Yen, Pham Nguyen Dong; Luong, Tran Thanh

    Structural and spectral properties of curcumin and metal- curcumin complex derived from turmeric (Curcuma longa) were studied by SEM and vibrational (FTIR and Raman) techniques. By comparison between curcumin commercial, fresh turmeric and a yellow powder obtained via extraction and purification of turmeric, we have found that this insoluble powder in water is curcumin. The yellow compound could complex with certain ion metal and this metal-curcumin coloring complex is water soluble and capable of producing varying hues of the same colors and having antimicrobial, cytotoxicity activities for use in foodstuffs and pharmacy. The result also demonstrates that Micro-Raman spec-troscopy is a valuable non-destructive tool and fast for investigation of a natural plant even when occurring in low concentrations.

  7. Formation of novel transition metal hydride complexes with ninefold hydrogen coordination

    PubMed Central

    Takagi, Shigeyuki; Iijima, Yuki; Sato, Toyoto; Saitoh, Hiroyuki; Ikeda, Kazutaka; Otomo, Toshiya; Miwa, Kazutoshi; Ikeshoji, Tamio; Orimo, Shin-ichi

    2017-01-01

    Ninefold coordination of hydrogen is very rare, and has been observed in two different hydride complexes comprising rhenium and technetium. Herein, based on a theoretical/experimental approach, we present evidence for the formation of ninefold H- coordination hydride complexes of molybdenum ([MoH9]3−), tungsten ([WH9]3−), niobium ([NbH9]4−) and tantalum ([TaH9]4−) in novel complex transition-metal hydrides, Li5MoH11, Li5WH11, Li6NbH11 and Li6TaH11, respectively. All of the synthesized materials are insulated with band gaps of approximately 4 eV, but contain a sufficient amount of hydrogen to cause the H 1s-derived states to reach the Fermi level. Such hydrogen-rich materials might be of interest for high-critical-temperature superconductivity if the gaps close under compression. Furthermore, the hydride complexes exhibit significant rotational motions associated with anharmonic librations at room temperature, which are often discussed in relation to the translational diffusion of cations in alkali-metal dodecahydro-closo-dodecaborates and strongly point to the emergence of a fast lithium conduction even at room temperature. PMID:28287143

  8. METHOD FOR MANUFACTURING LAMINATED SHEETS FOR PROTECTION AGAINST RADIOACTIVE WASTES, AND PROTECTING AND PACKAGING MEANS MANUFACTURED WITH THESE SHEETS; Papierfabrik Wilhemstal Wilhelm Ernst

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    None

    1959-07-15

    A description is given of laminated sheet, consisting of a first layer of absorbing and preferably fibrous material (e.g., filter or blotting paper, or felt), a second layer of adhesive, impermeable, and hydrophobic material (e.g., wax, bitumen, a polyvinyl or polyacrylic compound, or a polyhydrocarbon), and a third (and fourth) layer of rigid material more or less impermeable to liquids (e.g., metal (aluminum), polyvinyl chloride, polyethylene, or cardboard). These sheets can be used for covering laboratory tables and walls, for radiation protection (manufacture of clothes, etc.), or for packaging radioactive waste (manufacture of boxes, bags, etc.). (NPO)

  9. Ultrafast Transient Absorption Spectroscopy of Polymer-Based Organophotoredox Catalysts Mimicking Transition-Metal Complexes

    NASA Astrophysics Data System (ADS)

    Jamhawi, Abdelqader; Paul, Anam C.; Smith, Justin D.; Handa, Sachin; Liu, Jinjun

    2017-06-01

    Transition-metal complexes of rare earth metals including ruthenium and iridium are most commonly employed as visible-light photocatalysts. Despite their highly important and broad applications, they have many disadvantages including high cost associated with low abundance in earth crust, potential toxicity, requirement of specialized ligands for desired activity, and difficulty in recycling of metal contents as well as associated ligands. Polymer-based organophotoredox catalysts are promising alternatives and possess unique advantages such as easier synthesis from inexpensive starting material, longer excited state life time, broad range of activity, sustainability, and recyclability. In this research talk, time-resolved photoluminescence and femtosecond transient absorption (TA) spectroscopy measurements of three novel polymer-based organophotoredox catalysts will be presented. By our synthetic team, their catalytic activity has been proven in some highly valuable chemical transformations, that otherwise require transition metal complexes. Time-resolved spectroscopic investigations have demonstrated that photoinduced processes in these catalysts are similar to the transition metal complexes. Especially, intramolecular vibrational relaxation, internal conversion, and intersystem crossing from the S1 state to the T1 state all occur on a sub-picosecond timescale. The long lifetime of the T1 state ( 2-3 microsecond) renders these polymers potent oxidizing and reducing agents. A spectroscopic and kinetic model has been developed for global fitting of TA spectra in both the frequency and time domains. Implication of the current ultrafast spectroscopy studies of these novel molecules to their roles in photocatalysis will be discussed.

  10. Ceramic TBS/porous metal compliant layer

    NASA Technical Reports Server (NTRS)

    Tolokan, Robert P.; Jarrabet, G. P.

    1992-01-01

    Technetics Corporation manufactures metal fiber materials and components used in aerospace applications. Our technology base is fiber metal porous sheet material made from sinter bonded metal fibers. Fiber metals have percent densities (metal content by volume) from 10 to 65 percent. Various topics are covered and include the following: fiber metal materials, compliant layer thermal bayer coatings (TBC's), pad properties, ceramic/pad TBC design, thermal shock rig, fabrication, and applications.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Gerlach, Joerg; Kessler, Lutz; Paul, Udo

    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 regressionmore » 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.« less

  12. Analytical methods for determination of free metal ion concentration, labile species fraction and metal complexation capacity of environmental waters: a review.

    PubMed

    Pesavento, Maria; Alberti, Giancarla; Biesuz, Raffaela

    2009-01-12

    Different experimental approaches have been suggested in the last few decades to determine metal species in complex matrices of unknown composition as environmental waters. The methods are mainly focused on the determination of single species or groups of species. The more recent developments in trace elements speciation are reviewed focusing on methods for labile and free metal determination. Electrochemical procedures with low detection limit as anodic stripping voltammetry (ASV) and the competing ligand exchange with adsorption cathodic stripping voltammetry (CLE-AdCSV) have been widely employed in metal distribution studies in natural waters. Other electrochemical methods such as stripping chronopotentiometry and AGNES seem to be promising to evaluate the free metal concentration at the low levels of environmental samples. Separation techniques based on ion exchange (IE) and complexing resins (CR), and micro separation methods as the Donnan membrane technique (DMT), diffusive gradients in thin-film gels (DGT) and the permeation liquid membrane (PLM), are among the non-electrochemical methods largely used in this field and reviewed in the text. Under appropriate conditions such techniques make possible the evaluation of free metal ion concentration.

  13. Pharmacological Evaluation of Naproxen Metal Complexes on Antinociceptive, Anxiolytic, CNS Depressant, and Hypoglycemic Properties

    PubMed Central

    Das, Narhari; Abdur Rahman, S. M.

    2016-01-01

    Purpose. The present study was designed to investigate the antinociceptive, anxiolytic, CNS depressant, and hypoglycemic effects of the naproxen metal complexes. Methods. The antinociceptive activity was evaluated by acetic acid-induced writhing method and radiant heat tail-flick method while anxiolytic activity was evaluated by elevated plus maze model. The CNS depressant activity of naproxen metal complexes was assessed using phenobarbitone-induced sleeping time test and the hypoglycemic test was performed using oral glucose tolerance test. Results. Metal complexes significantly (P < 0.001) reduced the number of abdominal muscle contractions induced by 0.7% acetic acid solution in a dose dependent manner. At the dose of 25 mg/kg body weight p.o. copper, cobalt, and zinc complexes exhibited higher antinociceptive activity having 59.15%, 60.56%, and 57.75% of writhing inhibition, respectively, than the parent ligand naproxen (54.93%). In tail-flick test, at both doses of 25 and 50 mg/kg, the copper, cobalt, silver, and zinc complexes showed higher antinociceptive activity after 90 minutes than the parent drug naproxen. In elevated plus maze (EPM) model the cobalt and zinc complexes of naproxen showed significant anxiolytic effects in dose dependent manner, while the copper, cobalt, and zinc complexes showed significant CNS depressant and hypoglycemic activity. Conclusion. The present study demonstrated that copper, cobalt, and zinc complexes possess higher antinociceptive, anxiolytic, CNS depressant, and hypoglycemic properties than the parent ligand. PMID:27478435

  14. Regio- and Stereochemical Control in Ocimene Polymerization by Half-Sandwich Rare-Earth Metal Dialkyl Complexes.

    PubMed

    Peng, Deqian; Du, Gaixia; Zhang, Pengfei; Yao, Bo; Li, Xiaofang; Zhang, Shaowen

    2016-06-01

    The polymerization of ocimene has been first achieved by half-sandwich rare-earth metal dialkyl complexes in combination with activator and Al(i) Bu3 . The regio- and stereoselectivity in the ocimene polymerization can be controlled by tuning the cyclopentadienyl ligand and the central metal of the complex. The chiral cyclopentadienyl-ligated Sc complex 1 prepares syndiotactic cis-1,4-polyocimene (cis-1,4-selectivity up to 100%, rrrr = 100%), while the corresponding Lu, Y, and Dy complexes 2-4 and the achiral pentamethylcyclopentadienyl Sc, Lu, and Y complexes 5-7 afford isotactic trans-1,2-polyocimenes (trans-1,2-selectivity up to 100%, mm = 100%). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Affinity to bovine serum albumin and anticancer activity of some new water-soluble metal Schiff base complexes

    NASA Astrophysics Data System (ADS)

    Asadi, Mozaffar; Asadi, Zahra; Zarei, Leila; Sadi, Somaye Barzegar; Amirghofran, Zahra

    2014-12-01

    Metal Schiff-base complexes show biological activity but they are usually insoluble in water so four new water-soluble metal Schiff base complexes of Na2[M(5-SO3-1,2-salben]; (5-SO3-1,2-salben denoted N,N";-bis(5-sulphosalicyliden)-1,2-diaminobenzylamine and M = Mg, Mn, Cu, Zn) were synthesized and characterized. The formation constants of the metal complexes were determined by UV-Vis absorption spectroscopy. The interaction of these complexes with bovine serum albumin (BSA) was studied by fluorescence spectroscopy. Type of quenching, binding constants, number of binding sites and binding stoichiometries were determined by fluorescence quenching method. The results showed that the mentioned complexes strongly bound to BSA. Thermodynamic parameters indicated that hydrophobic association was the major binding force and that the interaction was entropy driven and enthalpically disfavoured. The displacement experiment showed that these complexes could bind to the subdomain IIA (site I) of albumin. Furthermore the synchronous fluorescence spectra showed that the microenvironment of the tryptophan residues was not apparently changed. Based on the Förster theory of non-radiation energy transfer, the distance between the donor (Trp residues) and the acceptor metal complexes was obtained. The growth inhibitory effect of complexes toward the K562 cancer cell line was measured.

  16. Prediction of the thermodynamic properties of metal-arsenate and metal-arsenite aqueous complexes to high temperatures and pressures and some geological consequences

    NASA Astrophysics Data System (ADS)

    Marini, Luigi; Accornero, Marina

    2007-07-01

    The standard thermodynamic properties at 25°C, 1 bar (Δ G {f/o}, Δ H {f/o}, S o, C {P/o}, V o, ω) and the coefficients of the revised Helgeson-Kirkham-Flowers equations of state were evaluated for several aqueous complexes formed by dissolved metals and either arsenate or arsenite ions. The guidelines of Shock and Helgeson (Geochim Cosmochim Acta 52:2009-2036, 1988) and Sverjensky et al. (Geochim Cosmochim Acta 61:1359-1412, 1997) were followed and corroborated with alternative approaches, whenever possible. The SUPCRT92 computer code was used to generate the log K of the destruction reactions of these metal-arsenate and metal-arsenite aqueous complexes at pressures and temperatures required by the EQ3/6 software package, version 7.2b. Apart from the AlAsO{4/o} and FeAsO{4/o} complexes, our log K at 25°C, 1 bar are in fair agreement with those of Whiting (MS Thesis, Colorado School of Mines, Golden, CO, 1992). Moreover, the equilibrium constants evaluated in this study are in good to fair agreement with those determined experimentally for the Ca-dihydroarsenate and Ca-hydroarsenate complexes at 40°C (Mironov et al., Russ J Inorg Chem 40:1690, 1995) and for Fe(III)-hydroarsenate complex at 25°C (Raposo et al., J Sol Chem 35:79-94, 2006), whereas the disagreement with the log K measured for the Ca-arsenate complex at 40°C (Mironov et al., Russ J Inorg Chem 40:1690, 1995) might be due to uncertainties in this measured value. The implications of aqueous complexing between dissolved metals and arsenate/arsenite ions were investigated for seawater, high-temperature geothermal liquids and acid mine drainage and aqueous solutions deriving from mixing of acid mine waters and surface waters.

  17. Controlling magnetism of a complex metallic system using atomic individualism.

    PubMed

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

    2010-08-06

    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--Gd(5)Ge(4)--that resulted in a controlled alteration of the magnetism of this compound using precise chemical tools.

  18. 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.

  19. Development of a low energy micro sheet forming machine

    NASA Astrophysics Data System (ADS)

    Razali, A. R.; Ann, C. T.; Shariff, H. M.; Kasim, N. I.; Musa, M. A.; Ahmad, A. F.

    2017-10-01

    It is expected that with the miniaturization of materials being processed, energy consumption is also being `miniaturized' proportionally. The focus of this study was to design a low energy micro-sheet-forming machine for thin sheet metal application and fabricate a low direct current powered micro-sheet-forming machine. A prototype of low energy system for a micro-sheet-forming machine which includes mechanical and electronic elements was developed. The machine was tested for its performance in terms of natural frequency, punching forces, punching speed and capability, energy consumption (single punch and frequency-time based). Based on the experiments, the machine can do 600 stroke per minute and the process is unaffected by the machine's natural frequency. It was also found that sub-Joule of power was required for a single stroke of punching/blanking process. Up to 100micron thick carbon steel shim was successfully tested and punched. It concludes that low power forming machine is feasible to be developed and be used to replace high powered machineries to form micro-products/parts.

  20. An Investigation and Prediction of Springback of Sheet Metals under Cold Forming Condition

    NASA Astrophysics Data System (ADS)

    Elsayed, A.; Mohamed, M.; Shazly, M.; Hegazy, A.

    2017-12-01

    Low formability and springback especially at room temperature are known to be major obstacles to advancements in sheet metal forming industries. The integration of numerical simulation within the R&D activities of the automotive industries provides a significant development in overcoming these drawbacks. The aim of the present work is to model and predict the springback of a Galvanized low carbon steel automotive panel part. This part suffers from both positive and negative springback which physically measured using CMM. The objective is to determine the suitable forming process parameters that minimize and compensate the springback through robust FE model. The analysis of the springback was carried out following (Isotropic model and Yoshida - Uemori model) which are calibrated through cyclic stress strain curve. The material data of the Galvanized low carbon steel was implemented via lookup tables in the commercial finite element software Pam-Stamp(TM). Firstly, the FE model was validated using the deformed part which suffers from springback problem at the same forming condition. The FE results were compared with the measured experimental trails providing very good agreement. Secondly, the validated FE model was used to determine the suitable forming parameters which could minimise the springback of the deformed part.

  1. Electronic Structure and Bonding in Transition Metal Inorganic and Organometallic Complexes: New Basis Sets, Linear Semibridging Carbonyls and Thiocarbonyls, and Oxidative Addition of Molecular Hydrogen to Square - Iridium Complexes.

    NASA Astrophysics Data System (ADS)

    Sargent, Andrew Landman

    Approximate molecular orbital and ab initio quantum chemical techniques are used to investigate the electronic structure, bonding and reactivity of several transition metal inorganic and organometallic complexes. Modest-sized basis sets are developed for the second-row transition metal atoms and are designed for use in geometry optimizations of inorganic and organometallic complexes incorporating these atoms. The basis sets produce optimized equilibrium geometries which are slightly better than those produced with standard 3-21G basis sets, and which are significantly better than those produced with effective core potential basis sets. Linear semibridging carbonyl ligands in heterobimetallic complexes which contain a coordinatively unsaturated late transition metal center are found to accept electron density from, rather than donate electron density to, these centers. Only when the secondary metal center is a coordinatively unsaturated early transition metal center does the semibridging ligand donate electron density to this center. Large holes in the d shell around the metal center are more prominent and prevalent in early than in late transition metal centers, and the importance of filling in these holes outweighs the importance of mitigating the charge imbalance due to the dative metal-metal interaction. Semibridging thiocarbonyl ligands are more effective donors of electron density than the carbonyl ligands since the occupied donor orbitals of pi symmetry are higher in energy. The stereoselectivity of H_2 addition to d^8 square-planar transition metal complexes is controlled by the interactions between the ligands in the plane of addition and the concentrations of electronic charge around the metal center as the complex evolves from a four-coordinate to a six-coordinate species. Electron -withdrawing ligands help stabilize the five-coordinate species while strong electron donor ligands contribute only to the destabilizing repulsive interactions. The relative

  2. 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.

  3. Method for casting thin metal objects

    DOEpatents

    Pehrson, Brandon P; Moore, Alan F

    2015-04-14

    Provided herein are various embodiments of systems for casting thin metal plates and sheets. Typical embodiments include layers of mold cavities that are oriented vertically for casting the metal plates. In some embodiments, the mold cavities include a beveled edge such that the plates that are cast have a beveled edge. In some embodiments, the mold cavities are filled with a molten metal through an open horizontal edge of the cavity. In some embodiments, the mold cavities are filled through one or more vertical feed orifices. Further disclosed are methods for forming a thin cast metal plate or sheet where the thickness of the cast part is in a range from 0.005 inches to 0.2 inches, and the surface area of the cast part is in a range from 16 square inches to 144 square inches.

  4. Spectral characterization, cyclic voltammetry, morphology, biological activities and DNA cleaving studies of amino acid Schiff base metal(II) complexes

    NASA Astrophysics Data System (ADS)

    Neelakantan, M. A.; Rusalraj, F.; Dharmaraja, J.; Johnsonraja, S.; Jeyakumar, T.; Sankaranarayana Pillai, M.

    2008-12-01

    Metal complexes are synthesized with Schiff bases derived from o-phthalaldehyde (opa) and amino acids viz., glycine (gly) L-alanine (ala), L-phenylalanine (pal). Metal ions coordinate in a tetradentate or hexadentate manner with these N 2O 2 donor ligands, which are characterized by elemental analysis, molar conductance, magnetic moments, IR, electronic, 1H NMR and EPR spectral studies. The elemental analysis suggests the stoichiometry to be 1:1 (metal:ligand). Based on EPR studies, spin-Hamiltonian and bonding parameters have been calculated. The g-values calculated for copper complexes at 300 K and in frozen DMSO (77 K) indicate the presence of the unpaired electron in the d orbital. The evaluated metal-ligand bonding parameters showed strong in-plane σ- and π-bonding. X-ray diffraction (XRD) and scanning electron micrography (SEM) analysis provide the crystalline nature and the morphology of the metal complexes. The cyclic voltammograms of the Cu(II)/Mn(II)/VO(II) complexes investigated in DMSO solution exhibit metal centered electroactivity in the potential range -1.5 to +1.5 V. The electrochemical data obtained for Cu(II) complexes explains the change of structural arrangement of the ligand around Cu(II) ions. The biological activity of the complexes has been tested on eight bacteria and three fungi. Cu(II) and Ni(II) complexes show an increased activity in comparison to the controls. The metal complexes of opapal Schiff base were evaluated for their DNA cleaving activities with calf-thymus DNA (CT DNA) under aerobic conditions. Cu(II) and VO(II) complexes show more pronounced activity in presence of the oxidant.

  5. Highly efficient one-step synthesis of carbon encapsulated nanocrystals by the oxidation of metal π-complexes

    NASA Astrophysics Data System (ADS)

    Liu, Boyang; Shao, Yingfeng; Xiang, Xin; Zhang, Fuhua; Yan, Shengchang; Li, Wenge

    2017-08-01

    Various carbon encapsulated nanocrystals, including MnS and MnO, Cr2O3, MoO2, Fe7S8 and Fe3O4, and ZrO2, are prepared in one step and in situ by a simple and highly efficient synthesis approach. The nanocrystals have an equiaxed morphology and a median size smaller than 30 nm. Tens and hundreds of these nanocrystals are entirely encapsulated by a wormlike amorphous carbon shell. The formation of a core-shell structure depends on the strongly exothermic reaction of metal π-complexes with ammonium persulfate in an autoclave at below 200 °C. During the oxidation process, the generated significant amounts of heat will destroy the molecular structure of the metal π-complex and cleave the ligands into small carbon fragments, which further transform into an amorphous carbon shell. The central metal atoms are oxidized to metal oxide/sulfide nanocrystals. The formation of a core-shell structure is independent of the numbers of ligands and carbon atoms as well as the metal types, implying that any metal π-complex can serve as a precursor and that various carbon encapsulated nanocrystals can be synthesized by this method.

  6. Synthesis, structure, DNA/BSA binding and antibacterial studies of NNO tridentate Schiff base metal complexes

    NASA Astrophysics Data System (ADS)

    Sakthi, Marimuthu; Ramu, Andy

    2017-12-01

    A new salicylaldehyde derived 2,4-diiodo-6-((2-phenylaminoethylimino)methyl)phenol Schiff base(L) and its transition metal complexes of the type MLCl where, M = Cu(II), Ni(II), Co(II), Mn(II) and Zn(II) have been synthesized. The coordination mode of Schiff base holding NNO donor atoms with metal ions was well investigated by elemental analysis, ESI-mass as well as IR, UV-vis, CV and NMR spectral studies. The binding efficiency and mode of these complexes with biological macromolecules viz., herring sperm DNA (HS- DNA) and bovine serum albumin (BSA) have been explored through various spectroscopic techniques. The characteristic changes in absorption, emission and, circular dichroism spectra of the complexes with DNA indicate the noticeable interaction between them. From the all spectral information complexes could interact with DNA via non-intercalation mode of binding. The hyperchromisim in absorption band and hypochromisim in emission intensity of BSA with different complex concentrations shown significant information, and the binding affinity value has been predicted from Stern-Volmer plots. Further, all the complexes could cleave the circular plasmid pUC19 DNA efficiently by using an activator H2O2. The ligand and all metal(II) complexes showed good antibacterial activities. The molecular docking studies of the complexes with DNA were performed in order to make a comparison and conclusion with spectral technic results.

  7. Parametric analysis of plastic strain and force distribution in single pass metal spinning

    NASA Astrophysics Data System (ADS)

    Choudhary, Shashank; Tejesh, Chiruvolu Mohan; Regalla, Srinivasa Prakash; Suresh, Kurra

    2013-12-01

    Metal spinning also known as spin forming is one of the sheet metal working processes by which an axis-symmetric part can be formed from a flat sheet metal blank. Parts are produced by pressing a blunt edged tool or roller on to the blank which in turn is mounted on a rotating mandrel. This paper discusses about the setting up a 3-D finite element simulation of single pass metal spinning in LS-Dyna. Four parameters were considered namely blank thickness, roller nose radius, feed ratio and mandrel speed and the variation in forces and plastic strain were analysed using the full-factorial design of experiments (DOE) method of simulation experiments. For some of these DOE runs, physical experiments on extra deep drawing (EDD) sheet metal were carried out using En31 tool on a lathe machine. Simulation results are able to predict the zone of unsafe thinning in the sheet and high forming forces that are hint to the necessity for less-expensive and semi-automated machine tools to help the household and small scale spinning workers widely prevalent in India.

  8. Heterobimetallic coordination polymers involving 3d metal complexes and heavier transition metals cyanometallates

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Peresypkina, Eugenia V.; Samsonenko, Denis G.; Novosibirsk State University, Novosibirsk 630090

    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.more » 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.« less

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

    PubMed

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

    2014-12-30

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

  10. Combined effects of metal complexation and size expansion in the electronic structure of DNA base pairs

    NASA Astrophysics Data System (ADS)

    Brancolini, Giorgia; Di Felice, Rosa

    2011-05-01

    Novel DNA derivatives have been recently investigated in the pursuit of modified DNA duplexes to tune the electronic structure of DNA-based assemblies for nanotechnology applications. Size-expanded DNAs (e.g., xDNA) and metalated DNAs (M-DNA) may enhance stacking interactions and induce metallic conductivity, respectively. Here we explore possible ways of tailoring the DNA electronic structure by combining the aromatic size expansion with the metal-doping. We select the salient structures from our recent study on natural DNA pairs complexed with transition metal ions and consider the equivalent model configurations for xDNA pairs. We present the results of density functional theory electronic structure calculations of the metalated expanded base-pairs with various localized basis sets and exchange-correlation functionals. Implicit solvent and coordination water molecules are also included. Our results indicate that the effect of base expansion is largest in Ag-xGC complexes, while Cu-xGC complexes are the most promising candidates for nanowires with enhanced electron transfer and also for on-purpose modification of the DNA double-helix for signal detection.

  11. Synthesis of Unsupported d(1)-d(x) Oxido-Bridged Heterobimetallic Complexes Containing V(IV): A New Direction for Metal-to-Metal Charge Transfer.

    PubMed

    Wu, Xinyuan; Huang, Tao; Lekich, Travis T; Sommer, Roger D; Weare, Walter W

    2015-06-01

    Heterobimetallic complexes composed only of first-row transition metals [(TMTAA)V(IV)═O→M(II)Py5Me2](OTf)2 (TMTAA = 7,16-dihydro-6,8,15,17-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine; Py5Me2 = 2,6-bis(1,1-bis(2-pyridyl)ethyl)pyridine; M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II); OTf = trifluoromethanesulfonate) have been synthesized through a dative interaction between a terminal oxido and M(II) metal centers. This is the first series of V(IV)═O→M(II) heterobimetallic complexes containing an unsupported oxido bridge. Among these five complexes, only V(IV)═O→Fe(II) (3b) has a clear new absorption band upon formation of the dinuclear species (502 nm, ε = 1700 M(-1) cm(-1)). This feature is assigned to a metal-to-metal charge transfer (MMCT) transition from V(IV) to Fe(II), which forms a V(V)-O-Fe(I) excited state. This assignment is supported by electrochemical data, electronic absorption profiles, and resonance Raman spectroscopy and represents the first report of visible-light induced MMCT in a heterobimetallic oxido-bridged molecule where the electron originates on a d(1) metal center.

  12. Lanthanide and transition metal complexes of bioactive coumarins: molecular modeling and spectroscopic studies.

    PubMed

    Georgieva, I; Mihaylov, Tz; Trendafilova, N

    2014-06-01

    The present paper summarizes theoretical and spectroscopic investigations on a series of active coumarins and their lanthanide and transition metal complexes with application in medicine and pharmacy. Molecular modeling as well as IR, Raman, NMR and electronic spectral simulations at different levels of theory were performed to obtain important molecular descriptors: total energy, formation energy, binding energy, stability, conformations, structural parameters, electron density distribution, molecular electrostatic potential, Fukui functions, atomic charges, and reactive indexes. The computations are performed both in gas phase and in solution with consideration of the solvent effect on the molecular structural and energetic parameters. The investigations have shown that the advanced computational methods are reliable for prediction of the metal-coumarin binding mode, electron density distribution, thermodynamic properties as well as the strength and nature of the metal-coumarin interaction (not experimentally accessible) and correctly interpret the experimental spectroscopic data. Known results from biological tests for cytotoxic, antimicrobial, anti-fungal, spasmolytic and anti-HIV activities on the studied metal complexes are reported and discussed. Copyright © 2014 Elsevier Inc. All rights reserved.

  13. Joining of aluminum sheet and glass fiber reinforced polymer using extruded pins

    NASA Astrophysics Data System (ADS)

    Conte, Romina; Buhl, Johannes; Ambrogio, Giuseppina; Bambach, Markus

    2018-05-01

    The present contribution proposes a new approach for joining sheet metal and fiber reinforced composites. The joining process draws upon a Friction Stir Forming (FSF) process, which is performed on the metal sheet to produce slender pins. These pins are used to pierce through the composite. Joining is complete by forming a locking head out of the part if the pin sticks out of the composite. Pins of different diameters and lengths were produced from EN AW-1050 material, which were joined to glass fiber reinforced polyamide-6. The strength of the joint has been experimentally tested in order to understand the effect of the process temperature on the pins strength and therefore on the joining. The results demonstrate the feasibility of this new technique, which uses no excess material.

  14. Isometric immersions and self-similar buckling in elastic sheets.

    NASA Astrophysics Data System (ADS)

    Gemmer, John

    The edges of torn elastic sheets and growing leaves often display hierarchical self-similar like buckling patterns. On the one hand, such complex, self similar patterns are usually associated with a competition between two distinct energy scales, e.g. elastic sheets with boundary conditions that preclude the possibility of relieving in plane strains, or at alloy-alloy interfaces between distinct crystal structures. On the other hand, within the non-Euclidean plate theory this complex morphology can be understood as low bending energy isometric immersions of hyperbolic Riemannian metrics. In particular, many growth patterns generate residual in-plane strains which can be entirely relieved by the sheet forming part of a surface of revolution or a helix. In this talk we will show that this complex morphology (i) arises from isometric immersions (ii) is driven by a competition between the two principal curvatures, rather than between bending and stretching. We identify the key role of branch-point (or monkey-saddle) singularities, in complex wrinkling patterns within the class of finite bending energy isometric immersions. Using these defects we will give an explicit construction of strain-free embeddings of hyperbolic surfaces that are fractal like and have lower elastic energy than their smooth counterparts US-Israel BSF Grant 2008432. NSF Grant DMS-0807501. NSF-RTG Grant DMS-1148284.

  15. Monitoring concept for structural integration of PZT-fiber arrays in metal sheets: a numerical and experimental study

    NASA Astrophysics Data System (ADS)

    Drossel, Welf-Guntram; Schubert, Andreas; Putz, Matthias; Koriath, Hans-Joachim; Wittstock, Volker; Hensel, Sebastian; Pierer, Alexander; Müller, Benedikt; Schmidt, Marek

    2018-01-01

    The technique joining by forming allows the structural integration of piezoceramic fibers into locally microstructured metal sheets without any elastic interlayers. A high-volume production of the joining partners causes in statistical deviations from the nominal dimensions. A numerical simulation on geometric process sensitivity shows that the deviations have a high significant influence on the resulting fiber stresses after the joining by forming operation and demonstrate the necessity of a monitoring concept. On this basis, the electromechanical behavior of piezoceramic array transducers is investigated experimentally before, during and after the joining process. The piezoceramic array transducer consists of an arrangement of five electrical interconnected piezoceramic fibers. The findings show that the impedance spectrum depends on the fiber stresses and can be used for in-process monitoring during the joining process. Based on the impedance values the preload state of the interconnected piezoceramic fibers can be specifically controlled and a fiber overload.

  16. Quantitative description and local structures of trivalent metal ions Eu(III) and Cm(III) complexed with polyacrylic acid.

    PubMed

    Montavon, G; Bouby, M; Huclier-Markai, S; Grambow, B; Geckeis, H; Rabung, T; Pashalidis, I; Amekraz, B; Moulin, C

    2008-11-15

    The trivalent metal ion (M(III)=Cm, Eu)/polyacrylic acid (PAA) system was studied in the pH range between 3 and 5.5 for a molar PAA-to-metal ratio above 1. The interaction was studied for a wide range of PAA (0.05 mg L(-1)-50 g L(-1)) and metal ion concentrations (2x10(-9)-10(-3) M). This work aimed at 3 goals (i) to determine the stoichiometry of M(III)-PAA complexes, (ii) to determine the number of complexed species and the local environment of the metal ion, and (iii) to quantify the reaction processes. Asymmetric flow-field-flow fractionation (AsFlFFF) coupled to ICP-MS evidenced that size distributions of Eu-PAA complexes and PAA were identical, suggesting that Eu bound to only one PAA chain. Time-resolved laser fluorescence spectroscopy (TRLFS) measurements performed with Eu and Cm showed a continuous shift of the spectra with increasing pH. The environment of complexed metal ions obviously changes with pH. Most probably, spectral variations arose from conformational changes within the M(III)-PAA complex due to pH variation. Complexation data describing the distribution of complexed and free metal ion were measured with Cm by TRLFS. They could be quantitatively described in the whole pH-range studied by considering the existence of only a single complexed species. This indicates that the slight changes in M(III) speciation with pH observed at the molecular level do not significantly affect the intrinsic binding constant. The interaction constant obtained from the modelling must be considered as a mean interaction constant.

  17. Preforming of polydioxanone sheets for orbital wall fractures - A technical note.

    PubMed

    Kruber, Daniel; Hierl, Thomas; Doerfler, Hans-Martin; Huempfner-Hierl, Heike; Krause, Matthias

    2018-07-01

    Polydioxanone (PDS) sheets are commonly used in the treatment of orbital wall fractures. A potential drawback of PDS is that it may be difficult to adapt to the anatomy of the orbital walls. Therefore a study was conceived to test the feasibility of preforming PDS sheets. PDS sheet material was water-heated and preformed using a template based on a statistical anatomical model. Then the deformed sheet was cooled, stored and compared to the original model to investigate post-deformation changes. PDS sheet material could easily be deformed using a mould. No significant post-cooling shape changes were noticed. PDS sheet material can be preformed into complex geometric shapes. This could be a benefit in the treatment of orbital wall fractures. Copyright © 2018 European Association for Cranio-Maxillo-Facial Surgery. Published by Elsevier Ltd. All rights reserved.

  18. Nanoscale Strontium Titanate Sheets and Crystals

    NASA Astrophysics Data System (ADS)

    Tilka, Jack Andrew

    The physical properties of materials are dominated by their structure and composition. Insight into the structure of complex oxide materials has the potential to improve our understanding and eventually control of their physical properties. This PhD thesis reports the development of characterization and fabrication techniques relevant to improving the scientific understanding of complex oxide materials. The work presented here has two components. I report a way to use ideas that were originally developed in semiconductor processing to control the elastic strain state and crystallization process of the model complex oxide SrTiO3. An additional component is an important series of advances in the analysis of diffraction patterns acquired with focused x-ray nanobeams. The fabrication and characterization of nanoscale SrTiO3 has been experimentally shown to allow the introduction of elastic strain into SrTiO3. The creation of thin SrTiO3 crystals from (001)-oriented SrTiO3 bulk single crystals using focused ion beam milling techniques yields sheets with submicron thickness and arbitrary orientation within the (001) plane. Synchrotron x-ray nanodiffraction experiments show that the SrTiO 3 sheets have rocking curves with angular widths less than 0.02°. These widths are less than a factor of two larger than bulk SrTiO3, which shows that the sheets are suitable substrates for epitaxial thin film growth. A precisely selected elastic strain can be introduced into the SrTiO 3 sheets using a silicon nitride stressor layer. Synchrotron x-ray nanodiffraction studies show that the strain introduced in the SrTiO3 sheets is on the order of 10-4, matching the predictions of an elastic model. This approach to elastic strain sharing in complex oxides allows the strain to be selected within a wide and continuous range of values, an effect not achievable in heteroepitaxy on rigid substrates. An additional fabrication technique is also evaluated here based on the crystallization of Sr

  19. Multiheteromacrocycles that Complex Metal Ions. Ninth Progress Report (includes results of last three years), 1 May 1980 -- 30 April 1983

    DOE R&D Accomplishments Database

    Cram, D. J.

    1982-09-15

    The overall objective of this research is to design, synthesize, and evaluate cyclic and polycyclic host organic compounds for the 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; numbers of binding sites; characters of binding sites; and valences. The hope is to synthesize new classes of compounds useful in the separation of metal ions, their complexes, and their clusters.

  20. Complexation- and ligand-induced metal release from 316L particles: importance of particle size and crystallographic structure.

    PubMed

    Hedberg, Yolanda; Hedberg, Jonas; Liu, Yi; Wallinder, Inger Odnevall

    2011-12-01

    Iron, chromium, nickel, and manganese released from gas-atomized AISI 316L stainless steel powders (sized <45 and <4 μm) were investigated in artificial lysosomal fluid (ALF, pH 4.5) and in solutions of its individual inorganic and organic components to determine its most aggressive component, elucidate synergistic effects, and assess release mechanisms, in dependence of surface changes using atomic absorption spectroscopy, Raman, XPS, and voltammetry. Complexation is the main reason for metal release from 316L particles immersed in ALF. Iron was mainly released, while manganese was preferentially released as a consequence of the reduction of manganese oxide on the surface. These processes resulted in highly complexing media in a partial oxidation of trivalent chromium to hexavalent chromium on the surface. The extent of metal release was partially controlled by surface properties (e.g., availability of elements on the surface and structure of the outermost surface) and partially by the complexation capacity of the different metals with the complexing agents of the different media. In general, compared to the coarse powder (<45 μm), the fine (<4 μm) powder displayed significantly higher released amounts of metals per surface area, increased with increased solution complexation capacity, while less amounts of metals were released into non-complexing solutions. Due to the ferritic structure of lower solubility for nickel of the fine powder, more nickel was released into all solutions compared with the coarser powder.

  1. Metal (II) Complexes Derived from Naphthofuran-2-carbohydrazide and Diacetylmonoxime Schiff Base: Synthesis, Spectroscopic, Electrochemical, and Biological Investigation

    PubMed Central

    Sumathi, R. B.; Halli, M. B.

    2014-01-01

    A new Schiff base and a new series of Co(II), Ni(II), Cu(II), Cd(II), and Hg(II) complexes were synthesized by the condensation of naphthofuran-2-carbohydrazide and diacetylmonoxime. Metal complexes of the Schiff base were prepared from their chloride salts of Co(II), Ni(II), Cu(II), Cd(II), and Hg(II) in ethanol. The ligand along with its metal complexes have been characterized on the basis of analytical data, IR, electronic, mass, 1HNMR, ESR spectral data, thermal studies, magnetic susceptibility, and molar conductance measurements. The nonelectrolytic behaviour of the complexes was assessed from the measured low conductance data. The elemental analysis of the complexes confirm the stoichiometry of the type CuL2Cl2 and MLCl2 where M = Ni(II), Co(II), Cd(II), and Hg(II) and L = Schiff base. The redox property of the Cu(II) complex was investigated by electrochemical method using cyclic voltammetry. In the light of these results, Co(II), Ni(II), and Cu(II) complexes are assigned octahedral geometry, Cd(II), and Hg(II) complexes tetrahedral geometry. In order to evaluate the effect of metal ions upon chelation, both the ligand and its metal complexes were screened for their antibacterial and antifungal activities by minimum inhibitory concentration (MIC) method. The DNA cleaving capacity of all the complexes was analysed by agarose gel electrophoresis method. PMID:24592203

  2. The importance of the Maillard-metal complexes and their silicates in astrobiology

    NASA Astrophysics Data System (ADS)

    Liesch, Patrick J.; Kolb, Vera M.

    2007-09-01

    The Maillard reaction occurs when sugars and amino acids are mixed together in the solid state or in the aqueous solution. Since both amino acids and sugar-like compounds are found on meteorites, we hypothesized that they would also undergo the Maillard reaction. Our recent work supports this idea. We have shown previously that the water-insoluble Maillard products have substantial similarities with the insoluble organic materials from the meteorites. The Maillard organic materials are also part of the desert varnish on Earth, which is a dark, shiny, hard rock coating that contains iron and manganese and is glazed in silicate. Rocks that are similar in appearance to the desert varnish have been observed on the Martian surface. They may also contain the organic materials. We have undertaken study of the interactions between the Maillard products, iron and other metals, and silicates, to elucidate the role of the Maillard products in the chemistry of desert varnish and meteorites. Specifically, we have synthesized a series of the Maillard-metal complexes, and have tested their reactivity towards silicates. We have studied the properties of these Maillard-metal-silicate products by the IR spectroscopy. The astrobiological potential of the Maillard-metal complexes is assessed.

  3. A modular tooling set-up for incremental sheet forming (ISF) with subsequent stress-relief annealing under partial constraints

    NASA Astrophysics Data System (ADS)

    Maqbool, Fawad; Bambach, Markus

    2017-10-01

    Incremental sheet forming (ISF) is a manufacturing process most suitable for small-batch production of sheet metal parts. In ISF, a CNC-controlled tool moves over the sheet metal, following a specified contour to form a part of the desired geometry. This study focuses on one of the dominant process limitations associated with the ISF, i.e., the limited geometrical accuracy. In this regard, a case study is performed which shows that increased geometrical accuracy of the formed part can be achieved by a using stress-relief annealing before unclamping. To keep the tooling costs low, a modular die design consisting of a stiff metal frame and inserts made from inexpensive plastics (Sika®) were devised. After forming, the plastics inserts are removed. The metal frame supports the part during stress-relief annealing. Finite Element (FE) simulations of the manufacturing process are performed. Due to the residual stresses induced during the forming, the geometry of the formed part, from FE simulation and the actual manufacturing process, shows severe distortion upon unclamping the part. Stress relief annealing of the formed part under partial constraints exerted by the tool frame shows that a part with high geometrical accuracy can be obtained.

  4. Biodegradation of Metal-EDTA Complexes by an Enriched Microbial Population

    PubMed Central

    Thomas, Russell A. P.; Lawlor, Kirsten; Bailey, Mark; Macaskie, Lynne E.

    1998-01-01

    A mixed culture utilizing EDTA as the sole carbon source was isolated from a mixed inoculum of water from the River Mersey (United Kingdom) and sludge from an industrial effluent treatment plant. Fourteen component organisms were isolated from the culture, including representatives of the genera Methylobacterium, Variovorax, Enterobacter, Aureobacterium, and Bacillus. The mixed culture biodegraded metal-EDTA complexes slowly; the biodegradability was in the order Fe>Cu>Co>Ni>Cd. By incorporation of inorganic phosphate into the medium as a precipitant ligand, heavy metals were removed in parallel to EDTA degradation. The mixed culture also utilized a number of possible EDTA degradation intermediates as carbon sources. PMID:9546167

  5. Synthesis of metal complexes involving Schiff base ligand with methylenedioxy moiety: spectral, thermal, XRD and antimicrobial studies.

    PubMed

    Sundararajan, M L; Jeyakumar, T; Anandakumaran, J; Karpanai Selvan, B

    2014-10-15

    Metal complexes of Zn(II), Cd(II), Ni(II), Cu(II), Fe(III), Co(II), Mn(II) Hg(II), and Ag(I) have been synthesized from Schiff base ligand, prepared by the condensation of 3,4-(methylenedioxy)aniline and 5-bromo salicylaldehyde. All the compounds have been characterized by using elemental analysis, molar conductance, FT-IR, UV-Vis, (1)H NMR, (13)C NMR, mass spectra, powder XRD and thermal analysis (TG/DTA) technique. The elemental analysis suggests the stoichiometry to be 1:1 (metal:ligand). The FT-IR, (1)H NMR, (13)C NMR and UV-Vis spectral data suggest that the ligand coordinate to the metal atom by imino nitrogen and phenolic oxygen as bidentate manner. Mass spectral data further support the molecular mass of the compounds and their structure. Powder XRD indicates the crystalline state and morphology of the ligand and its metal complexes. The thermal behaviors of the complexes prove the presence of lattice as well as coordinated water molecules in the complexes. Melting point supports the thermal stability of all the compounds. The in vitro antimicrobial effects of the synthesized compounds were tested against five bacterial and three fungal species by well diffusion method. Antioxidant activities have also been performed for all the compounds. Metal complexes show more biological activity than the Schiff base. Copyright © 2014 Elsevier B.V. All rights reserved.

  6. Synthesis, structure and DFT study of cymantrenyl Fischer carbene complexes of group VI and VII transition metals

    NASA Astrophysics Data System (ADS)

    Fraser, Roan; van Rooyen, Petrus H.; Landman, Marilé

    2016-02-01

    Bi- and trimetallic carbene complexes of group VI and VII transition metals (Cr, Mo, W, Mn and Re), with CpMn(CO)3 as the initial synthon, have been synthesised according to the classical Fischer methodology. Crystal structures of the novel carbene complexes with general formula [Mx(CO)y-1{C(OEt)(MnCp(CO)3)}], where x = 1 then y = 3 or 6; x = 2 then y = 10, of the complexes are reported. A density functional theory (DFT) study was undertaken to determine natural bonding orbitals (NBOs) and conformational as well as isomeric aspects of the polymetallic complexes. Application of the second-order perturbation theory (SOPT) of the natural bond orbital (NBO) method revealed stabilizing interactions between the methylene C-H bonds and the carbonyl ligands of the carbene metal moiety. These stabilization interactions show a linear decrease for the group VI metal carbene complexes down the group.

  7. Crown Ether Complexes of Alkali-Metal Chlorides from SO2.

    PubMed

    Reuter, Kirsten; Rudel, Stefan S; Buchner, Magnus R; Kraus, Florian; von Hänisch, Carsten

    2017-07-18

    The structures of alkali-metal chloride SO 2 solvates (Li-Cs) in conjunction with 12-crown-4 or 1,2-disila-12-crown-4 show strong discrepancies, despite the structural similarity of the ligands. Both types of crown ethers form 1:1 complexes with LiCl to give [Li(1,2-disila-12-crown-4)(SO 2 Cl)] (1) and [Li(12-crown-4)Cl]⋅4 SO 2 (2). However, 1,2-disila-12-crown-4 proved unable to coordinate cations too large for the cavity diameter, for example, by the formation of sandwich-type complexes. As a result, 12-crown-4 reacts exclusively with the heavier alkali-metal chlorides NaCl, KCl and RbCl. Compounds [Na(12-crown-4) 2 ]Cl⋅4 SO 2 (3) and [M(12-crown-4) 2 (SO 2 )]Cl⋅4 SO 2 (4: M=K; 5: M=Rb) all showed S-coordination to the chloride ions through four SO 2 molecules. Compounds 4 and 5 additionally exhibit the first crystallographically confirmed non-bridging O,O'-coordination mode of SO 2 . Unexpectedly, the disila-crown ether supports the dissolution of RbCl and CsCl in the solvent and gives the homoleptic SO 2 -solvated alkali-metal chlorides [MCl⋅3 SO 2 ] (6: M=Rb; 7: M=Cs), which incorporate bridging μ-O,O'-coordinating moieties and the unprecedented side-on O,O'-coordination mode. All compounds were characterised by single-crystal X-ray diffraction. The crown ether complexes were additionally studied by using NMR spectroscopy, and the presence of SO 2 at ambient temperature was revealed by IR spectroscopy of the neat compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Parametrization of a force field for metals complexed to biomacromolecules: applications to Fe(II), Cu(II) and Pb(II)

    NASA Astrophysics Data System (ADS)

    David, Laurent; Amara, Patricia; Field, Martin J.; Major, François

    2002-08-01

    Although techniques for the simulation of biomolecules, such as proteins and RNAs, have greatly advanced in the last decade, modeling complexes of biomolecules with metal ions remains problematic. Precise calculations can be done with quantum mechanical methods but these are prohibitive for systems the size of macromolecules. More qualitative modeling can be done with molecular mechanical potentials but the parametrization of force fields for metals is often difficult, particularly if the bonding between the metal and the groups in its coordination shell has significant covalent character. In this paper we present a method for deriving bond and bond-angle parameters for metal complexes from experimental bond and bond-angle distributions obtained from the Cambridge Structural Database. In conjunction with this method, we also introduce a non-standard energy term of gaussian form that allows us to obtain a stable description of the coordination about a metal center during a simulation. The method was evaluated on Fe(II)-porphyrin complexes, on simple Cu(II) ion complexes and a number of complexes of the Pb(II) ion.

  9. Development of Hydrogen Storage Tank Systems Based on Complex Metal Hydrides

    PubMed Central

    Ley, Morten B.; Meggouh, Mariem; Moury, Romain; Peinecke, Kateryna; Felderhoff, Michael

    2015-01-01

    This review describes recent research in the development of tank systems based on complex metal hydrides for thermolysis and hydrolysis. Commercial applications using complex metal hydrides are limited, especially for thermolysis-based systems where so far only demonstration projects have been performed. Hydrolysis-based systems find their way in space, naval, military and defense applications due to their compatibility with proton exchange membrane (PEM) fuel cells. Tank design, modeling, and development for thermolysis and hydrolysis systems as well as commercial applications of hydrolysis systems are described in more detail in this review. For thermolysis, mostly sodium aluminum hydride containing tanks were developed, and only a few examples with nitrides, ammonia borane and alane. For hydrolysis, sodium borohydride was the preferred material whereas ammonia borane found less popularity. Recycling of the sodium borohydride spent fuel remains an important part for their commercial viability. PMID:28793541

  10. Development of inexpensive metal macrocyclic complexes for use in fuel cells

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Doddapaneni, N.; Ingersoll, D.; Kosek, J.A.

    Several metal macrocyclic complexes were synthesized for use as catalysts in fuel cells. An initial evaluation of their ability to catalyze the fuel cell reactions were completed. Based on this initial evaluation, one metal macrocyclic catalyst was selected and long-term stability testing in a fuel cell was initiated. The fuel cell employing this catalyst was operated continuously for one year with little signs of catalyst degradation. The effect of synthetic reformates on the performance of the catalyst in the fuel cell environment also demonstrated high tolerance of this catalyst for common contaminants and poisons.

  11. Structural assessment of metal foam using combined NDE and FEA

    NASA Astrophysics Data System (ADS)

    Ghosn, Louis J.; Abdul-Aziz, Ali; Young, Philippe G.; Rauser, Richard W.

    2005-05-01

    Metal foams are expected to find use in structural applications where weight is of particular concern, such as space vehicles, rotorcraft blades, car bodies or portable electronic devices. The obvious structural application of metal foam is for light weight sandwich panels, made up of thin solid face sheets and a metallic foam core. The stiffness of the sandwich structure is increased by separating the two face sheets by a light weight foam core. The resulting high-stiffness structure is lighter than that constructed only out of the solid metal material. Since the face sheets carry the applied in-plane and bending loads, the sandwich architecture is a viable engineering concept. However, the metal foam core must resist transverse shear loads and compressive loads while remaining integral with the face sheets. Challenges relating to the fabrication and testing of these metal foam panels remain due to some mechanical properties falling short of their theoretical potential. Theoretical mechanical properties are based on an idealized foam microstructure and assumed cell geometry. But the actual testing is performed on as fabricated foam microstructure. Hence in this study, a high fidelity finite element analysis is conducted on as fabricated metal foam microstructures, to compare the calculated mechanical properties with the idealized theory. The high fidelity geometric models for the FEA are generated using series of 2D CT scans of the foam structure to reconstruct the 3D metal foam geometry. The metal foam material is an aerospace grade precipitation hardened 17-4 PH stainless steel with high strength and high toughness. Tensile, compressive, and shear mechanical properties are deduced from the FEA model and compared with the theoretical values. The combined NDE/FEA provided insight in the variability of the mechanical properties compared to idealized theory.

  12. Electromagnetic flat sheet forming by spiral type actuator coil

    NASA Astrophysics Data System (ADS)

    Akbar, S.; Aleem, M. A.; Sarwar, M. N.; Zillohu, A. U.; Awan, M. S.; Haider, A.; Ahmad, Z.; Akhtar, S.; Farooque, M.

    2016-08-01

    Focus of present work is to develop a setup for high strain rate electromagnetic forming of thin aluminum sheets (0.5, 1.0, 1.5 and 2.0 mm) and optimization of forming parameters. Flat spiral coil of 99.9% pure Cu strip (2.5x8.0 mm) with self-inductance 11 μH, 13 no. of turns and resultant outer diameter of 130mm has been fabricated and was coupled to a capacitor bank of energy, voltage and capacitance of 9 kJ, 900 V and 22.8 mF, respectively. To optimize the coil design, a commercially available software FEMM-4.2 was used to simulate the electromagnetic field profile generated by the coils of different pitch but same number of turns. Results of electromagnetic field intensity proposed by simulation agree in close proximity with those of theoretical as well as experimental data. The calculation of electromagnetic force and magnetic couplings between the coil and metal sheet are made. Forming parameters were optimized for different sheet thicknesses. Electromagnetic field intensity's profile plays a principal role in forming of typical shapes and patterns in sheets.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Moeller,P.; Beauchesne, K.; Huncik, K.

    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 inmore » 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.« less

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Moeller, P.D.R.; Beauchesne, K.R.; Huncik, K.M.

    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 inmore » 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.« less

  15. Synthesis, characterization and molecular modeling of some transition metal complexes of Schiff base derived from 5-aminouracil and 2-benzoyl pyridine

    NASA Astrophysics Data System (ADS)

    Abdel-Monem, Yasser K.; Abouel-Enein, Saeyda A.; El-Seady, Safa M.

    2018-01-01

    Multidentate Schiff base (H2L) ligand results from condensation of 5-aminouracil and 2-benzoyl pyridine and its metal chloride (Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Pd(II), Fe(III), Cr(III), Ru(III), Zr(IV) and Hf(IV)) complexes were prepared. The structural features of the ligand and its metal complexes were confirmed by elemental analyses, spectroscopic methods (IR, UV-Vis, 1H NMR, mass), magnetic moment measurements and thermal studies. The data refer to the ligand coordinates with metal ions in a neutral form and shows different modes of chelation toward the metal atom. All complexes have octahedral skeleton structure, tetrahedrally Mn(II), Ni(II), trigonalbipyramidal Co(II) and square planner Pd(II). Thermal decomposition of complexes as well as the interaction of different types of solvent of crystallization are assigned by thermogravimetric analysis. Molecular modeling of prepared complexes were investigated to study the expected anticancer activities of the prepared complexes. All metal complexes have no interaction except the complexes of Pd(II), Fe(III) and Mn(II).

  16. Comparison of the toxicity of some metals and their tetracyanide complexes on the respiration of non acclimated activated sludges.

    PubMed

    Morozzi, G; Cenci, G

    1978-12-01

    The toxic effect of the metal ions of cadmium, zinc, nickel and mercury and their tetracyanide salt complexes, on the activated sludge not previously acclimated, has been studied. The evaluation of the effect was carried out using both the Warburg and TTC-method. The results obtained have shown that the toxicity of the cadmium and zinc complexes is higher than that of the corresponding metals, while the toxicity of Ni(CN)4(2-) is lower than that of the corresponding metals. No differences have been found between the effect of mercury and the corresponding tetracyanide complex. From the data obtained it appears that it is not possible to generalize about the biological effect of complexation with the CN- group, but it should be stated that, generally, there are substantial differences between metals and their cyanide complexes as far as toxicity for activated sludge is concerned.

  17. Synthesis, spectral, thermal and antimicrobial studies of transition metal complexes of 14-membered tetraaza[N4] macrocyclic ligand

    NASA Astrophysics Data System (ADS)

    Shankarwar, Sunil G.; Nagolkar, Bhagwat B.; Shelke, Vinod A.; Chondhekar, Trimbak K.

    2015-06-01

    A series of metal complexes of Mn(II), Co(II), Ni(II), Cu(II), have been synthesized with newly synthesized biologically active macrocyclic ligand. The ligand was synthesized by condensation of β-diketone 1-(4-chlorophenyl)-3-(2-hydroxyphenyl)propane-1,3-dione and o-phenylene diamine. All the complexes were characterized by elemental analysis, molar conductivity, magnetic susceptibility, thermal analysis, X-ray diffraction, IR, 1H-NMR, UV-Vis spectroscopy and mass spectroscopy. From the analytical data, stoichiometry of the complexes was found to be 1:2 (metal:ligand). Thermal behavior (TG/DTA) and kinetic parameters suggest more ordered activated state in complex formation. All the complexes are of high spin type and six coordinated. On the basis of IR, electronic spectral studies and magnetic behavior, an octahedral geometry has been assigned to these complexes. The antibacterial and antifungal activities of the ligand and its metal complexes, has been screened in vitro against Staphylococcus aureus, Escherichia coli and Aspergillus niger, Trichoderma respectively.

  18. Parallel-multiplexed excitation light-sheet microscopy (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Xu, Dongli; Zhou, Weibin; Peng, Leilei

    2017-02-01

    Laser scanning light-sheet imaging allows fast 3D image of live samples with minimal bleach and photo-toxicity. Existing light-sheet techniques have very limited capability in multi-label imaging. Hyper-spectral imaging is needed to unmix commonly used fluorescent proteins with large spectral overlaps. However, the challenge is how to perform hyper-spectral imaging without sacrificing the image speed, so that dynamic and complex events can be captured live. We report wavelength-encoded structured illumination light sheet imaging (λ-SIM light-sheet), a novel light-sheet technique that is capable of parallel multiplexing in multiple excitation-emission spectral channels. λ-SIM light-sheet captures images of all possible excitation-emission channels in true parallel. It does not require compromising the imaging speed and is capable of distinguish labels by both excitation and emission spectral properties, which facilitates unmixing fluorescent labels with overlapping spectral peaks and will allow more labels being used together. We build a hyper-spectral light-sheet microscope that combined λ-SIM with an extended field of view through Bessel beam illumination. The system has a 250-micron-wide field of view and confocal level resolution. The microscope, equipped with multiple laser lines and an unlimited number of spectral channels, can potentially image up to 6 commonly used fluorescent proteins from blue to red. Results from in vivo imaging of live zebrafish embryos expressing various genetic markers and sensors will be shown. Hyper-spectral images from λ-SIM light-sheet will allow multiplexed and dynamic functional imaging in live tissue and animals.

  19. 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.

  20. Design of conveyor utilization monitoring system: a case study of powder coating line in sheet metal fabrication

    NASA Astrophysics Data System (ADS)

    Prasetyo, Hoedi; Sugiarto, Yohanes; Nur Rosyidi, Cucuk

    2018-03-01

    Conveyor is a very useful equipment to replace manpower in transporting the goods. It highly influences the productivity, production capacity utilization and eventually the production cost. This paper proposes a system to monitor the utilization of conveyor at a low cost through a case study at powder coating process line in a sheet metal fabrication. Preliminary observation was conducted to identify the problems. The monitoring system was then built and executed. The system consists of two sub systems. First is sub system for collecting and transmitting the required data and the second is sub system for displaying the data. The system utilizes sensors, wireless data transfer and windows-based application. The test results showed that the whole system works properly. By this system, the productivity and status of the conveyor can be monitored in real time. This research enriches the development of conveyor monitoring system especially for implementation in small and medium enterprises.

  1. Bessel light sheet structured illumination microscopy

    NASA Astrophysics Data System (ADS)

    Noshirvani Allahabadi, Golchehr

    Biomedical study researchers using animals to model disease and treatment need fast, deep, noninvasive, and inexpensive multi-channel imaging methods. Traditional fluorescence microscopy meets those criteria to an extent. Specifically, two-photon and confocal microscopy, the two most commonly used methods, are limited in penetration depth, cost, resolution, and field of view. In addition, two-photon microscopy has limited ability in multi-channel imaging. Light sheet microscopy, a fast developing 3D fluorescence imaging method, offers attractive advantages over traditional two-photon and confocal microscopy. Light sheet microscopy is much more applicable for in vivo 3D time-lapsed imaging, owing to its selective illumination of tissue layer, superior speed, low light exposure, high penetration depth, and low levels of photobleaching. However, standard light sheet microscopy using Gaussian beam excitation has two main disadvantages: 1) the field of view (FOV) of light sheet microscopy is limited by the depth of focus of the Gaussian beam. 2) Light-sheet images can be degraded by scattering, which limits the penetration of the excitation beam and blurs emission images in deep tissue layers. While two-sided sheet illumination, which doubles the field of view by illuminating the sample from opposite sides, offers a potential solution, the technique adds complexity and cost to the imaging system. We investigate a new technique to address these limitations: Bessel light sheet microscopy in combination with incoherent nonlinear Structured Illumination Microscopy (SIM). Results demonstrate that, at visible wavelengths, Bessel excitation penetrates up to 250 microns deep in the scattering media with single-side illumination. Bessel light sheet microscope achieves confocal level resolution at a lateral resolution of 0.3 micron and an axial resolution of 1 micron. Incoherent nonlinear SIM further reduces the diffused background in Bessel light sheet images, resulting in

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

    PubMed Central

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

    2014-01-01

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

  3. Multiheteromacrocycles that Complex Metal Ions. Second Progress Report, 1 May 1975 -- 30 April 1976

    DOE R&D Accomplishments Database

    Cram, D. J.

    1976-01-15

    Objective is to develop cyclic and polycyclic host organic compounds to complex and lipophilize metal ions. Macrorings were synthesized: (OCH{sub 2} CH{sub 2} O CH{sub 2}COCH{sub 2} COCH{sub 2}){sub 2} and (OCH{sub 2} CH{sub 2} O CH{sub 2} COCH{sub 2} COCH{sub 2}){sub 3}. The smaller ring complexes divalent metals 10{sup 1+9} times better than the open-chain model CH{sub 3} O CH{sub 2} CO CH{sub 2} COCH{sub 2} O CH{sub 3}, and the order in which metal ions are complexed is Cu{sup 2+}, UO{sub 2}{sup 2+} greater than Ni{sup 2+} greater than Fe{sup 2+}, Co{sup 2+}, Zn{sup 2+}, Cd{sup 2+} greater than Mn{sup 2+}. The UO{sub 2}{sup 2+} and Cu{sup 2+} complexes were isolated and characterized. The larger ring complexes trivalent metals 10{sup 0.9-1.7} times better than the open- chain model compound, and the order is La{sup 3+}, Ce{sup 3+} greater than Cr{sup 3+}. Five other macrocycles were also synthesized, and their binding constants with Na, K, NH{sub 4}, and Cs picrates were measured. Six compounds containing one macroring and two inward-pointing ArOH or ArOCH{sub 3} groups were also prepared and tested for binding of Li, Na, K, Rb, and NH{sub 4} picrates. Racemic compounds containing two binaphthyls and its sulfur analog were prepared. Cage-shaped multiheteromacrocycles containing ten O ligand sites or four S and six O ligand sites were prepared and the binding capability of the first compound for picrates studied. Two ring systems with phosphonate ester groups were also prepared. (DLC)

  4. Size, speciation and lability of NOM-metal complexes in hyperalkaline cave dripwater

    NASA Astrophysics Data System (ADS)

    Hartland, Adam; Fairchild, Ian J.; Lead, Jamie R.; Zhang, Hao; Baalousha, Mohammed

    2011-12-01

    . Integrated over the entire experiment, the DGT-available proportion of transition metals (Ni > Cu & V >> Co) differed greatly from the expected hierarchy from WHAM and MINTEQ, indicating unusually strong complexation of Co. Total metal concentrations of Cu, Ni, and Co in raw and filtered PE1 dripwater samples ( n = 53) were well correlated (Cu vs. Ni, R2 = 0.8; Cu vs. Co, R2 = 0.5) and were strongly reduced (> ca. 50%) by filtration at ca. 100 and 1 nm, indicating a common colloidal association. Our results demonstrate that soil-derived colloids reach speleothems, despite transport through a karst zone with potential for adsorption, and that NOM is a dominant complexant of trace metals in high pH speleothem-forming groundwaters.

  5. Vacuum forming of thermoplastic sheet results in low-cost investment casting patterns

    NASA Technical Reports Server (NTRS)

    Clarke, A. E., Jr.

    1964-01-01

    Vacuum forming of a sheet of thermoplastic material around a mandrel conforming to the shape of the finished object provides a pattern for an investment mold. The thickness of the metal part is determined by the thickness of the plastic pattern.

  6. Experimental analysis of Nd-YAG laser cutting of sheet materials - A review

    NASA Astrophysics Data System (ADS)

    Sharma, Amit; Yadava, Vinod

    2018-01-01

    Cutting of sheet material is considered as an important process due to its relevance among products of everyday life such as aircrafts, ships, cars, furniture etc. Among various sheet cutting processes (ASCPs), laser beam cutting is one of the most capable ASCP to create complex geometries with stringent design requirements in difficult-to-cut sheet materials. Based on the recent research work in the area of sheet cutting, it is found that the Nd-YAG laser is used for cutting of sheet material in general and reflective sheet material in particular. This paper reviews the experimental analysis of Nd-YAG laser cutting process, carried out to study the influence of laser cutting parameters on the process performance index. The significance of experimental modeling and different optimization approaches employed by various researchers has also been discussed in this study.

  7. Intracellular trafficking of a pH-responsive drug metal complex.

    PubMed

    Kheirolomoom, Azadeh; Ingham, Elizabeth S; Commisso, Joel; Abushaban, Neveen; Ferrara, Katherine W

    2016-12-10

    We previously developed a pH-responsive copper-doxorubicin (CuDox) cargo in lysolipid-based temperature-sensitive liposomes (LTSLs). The CuDox complex is released from the particle by elevated temperature; however, full release of doxorubicin from CuDox requires a reduced pH, such as that expected in lysosomes. The primary goal of this study is to evaluate the cellular uptake and intracellular trafficking of the drug-metal complex in comparison with intact liposomes and free drug. We found that the CuDox complex was efficiently internalized by mammary carcinoma cells after release from LTSLs. Intracellular doxorubicin and copper were 6-fold and 5-fold greater, respectively, after a 0.5h incubation with the released CuDox complex, as compared to incubation with intact liposomes containing the complex. Total cellular doxorubicin fluorescence was similar following CuDox and free doxorubicin incubation. Imaging and mass spectrometry assays indicated that the CuDox complex was initially internalized intact but breaks down over time within cells, with intracellular copper decreasing more rapidly than intracellular doxorubicin. Doxorubicin fluorescence was reduced when complexed with copper, and nuclear fluorescence was reduced when cells were incubated with the CuDox complex as compared with free doxorubicin. Therapeutic efficacy, which typically results from intercalation of doxorubicin with DNA, was equivalent for the CuDox complex and free doxorubicin and was superior to that of liposomal doxorubicin formulations. Taken together, the results suggest that quenched CuDox reaches the nucleus and remains efficacious. In order to design protocols for the use of these temperature-sensitive particles in cancer treatment, the timing of hyperthermia relative to drug administration must be examined. When cells were heated to 42°C prior to the addition of free doxorubicin, nuclear drug accumulation increased by 1.8-fold in cancer cells after 5h, and cytotoxicity increased 1

  8. A tritopic carbanionic N-heterocyclic dicarbene and its homo- and heterometallic coinage metal complexes.

    PubMed

    Zhang, Fan; Cao, Xiao-Ming; Wang, Jiwei; Jiao, Jiajun; Huang, Yongming; Shi, Min; Braunstein, Pierre; Zhang, Jun

    2018-05-21

    Homo (Au3)- and heterotrinuclear coinage metal complexes (Au2Ag and Au2Cu) ligated by the first tritopic carbanionic N-heterocyclic carbene (NHC) have been prepared by deprotonation of ditopic NHC digold complexes and structurally characterized by single-crystal X-ray diffraction.

  9. MOD silver metallization for photovoltaics

    NASA Technical Reports Server (NTRS)

    Vest, G. M.; Vest, R. W.

    1984-01-01

    Photovoltaic cells require back side metallization and a collector grid system on the front surface. Both front and back surface metallizations should have good adhesion, low contact resistance, low sheet resistance, long term stability, and their deposition methods should not degrade the n-p junction. Advantages and disadvantages of different deposition methods are discussed.

  10. Metals. Industrial Arts. Performance Objectives, Junior High School.

    ERIC Educational Resources Information Center

    Bunch, Edwood; And Others

    Several intermediate performance objectives and corresponding criterion measures are listed for a metals course for seventh, eighth, and ninth grade students. The seventh grade section includes 13 terminal objectives for a 9-week course and provides exploratory units in bench metals and sheet metals. Industrial materials and processes receive…

  11. Fast imaging of live organisms with sculpted light sheets

    NASA Astrophysics Data System (ADS)

    Chmielewski, Aleksander K.; Kyrsting, Anders; Mahou, Pierre; Wayland, Matthew T.; Muresan, Leila; Evers, Jan Felix; Kaminski, Clemens F.

    2015-04-01

    Light-sheet microscopy is an increasingly popular technique in the life sciences due to its fast 3D imaging capability of fluorescent samples with low photo toxicity compared to confocal methods. In this work we present a new, fast, flexible and simple to implement method to optimize the illumination light-sheet to the requirement at hand. A telescope composed of two electrically tuneable lenses enables us to define thickness and position of the light-sheet independently but accurately within milliseconds, and therefore optimize image quality of the features of interest interactively. We demonstrated the practical benefit of this technique by 1) assembling large field of views from tiled single exposure each with individually optimized illumination settings; 2) sculpting the light-sheet to trace complex sample shapes within single exposures. This technique proved compatible with confocal line scanning detection, further improving image contrast and resolution. Finally, we determined the effect of light-sheet optimization in the context of scattering tissue, devising procedures for balancing image quality, field of view and acquisition speed.

  12. Synthesis and structural studies of two pyridine-armed reinforced cyclen chelators and their transition metal complexes.

    PubMed

    Wilson, Kevin R; Cannon-Smith, Desiray J; Burke, Benjamin P; Birdsong, Orry C; Archibald, Stephen J; Hubin, Timothy J

    2016-08-16

    Two novel pyridine pendant-armed macrocycles structurally reinforced by an ethyl bridge, either between adjacent nitrogens (for side-bridged) or non-adjacent nitrogens (for cross-bridged), have been synthesized and complexed with a range of transition metal ions (Co 2+ , Ni 2+ , Cu 2+ and Zn 2+ ). X-ray crystal structures of selected cross-bridged complexes were obtained which showed the characteristic cis-V configuration with potential labile cis binding sites. The complexes have been characterized by their electronic spectra and magnetic moments, which show the expected high spin divalent metal complex in most cases. Exceptions are the nickel side-bridged complex, which shows a mixture of high-spin and low spin, and the cobalt cross-bridged complex which has oxidized to cobalt(III). Cyclic voltammetry in acetonitrile was carried out to assess the potential future use of these complexes in oxidation catalysis. Selected complexes offer significant catalytic potential enhanced by the addition of the pyridyl arm to a reinforced cyclen backbone.

  13. Metal based biologically active compounds: Design, synthesis, DNA binding and antidiabetic activity of 6-methyl-3-formyl chromone derived hydrazones and their metal (II) complexes.

    PubMed

    Philip, Jessica Elizabeth; Shahid, Muhammad; Prathapachandra Kurup, M R; Velayudhan, Mohanan Puzhavoorparambil

    2017-10-01

    Two chromone hydrazone ligands HL 1 and HL 2 were synthesized and characterized by elemental analyses, IR, 1 H NMR & 13 C NMR, electronic absorption and mass spectra. The reactions of the chromone hydrazones with transition metals such as Ni, Cu, and Zn (II) salts of acetate afforded mononuclear metal complexes. Characterization and structure elucidation of the prepared chromone hydrazone metal (II) complexes were done by elemental, IR, electronic, EPR spectra and thermo gravimetric analyses as well as conductivity and magnetic susceptibility measurements. The spectroscopic data showed that the ligand acts as a mono basic bidentate with coordination sites are azomethine nitrogen and hydrazonic oxygen, and they exhibited distorted geometry. The biological studies involved antidiabetic activity i.e. enzyme inhibition of α-amylase and α-glucosidase, Calf Thymus - DNA (CT-DNA) interaction and molecular docking. Potential capacity of synthesized compounds to inhibit the α-amylase and α-glucosidase activity was assayed whereas DNA interaction studies were carried out with the help UV-Vis absorption titration and viscosity method. The docking studies of chromone hydrazones show that they are minor groove binders. Complexes were found to be good DNA - intercalates. Chromone hydrazones and its transition metal complexes have shown comparable antidiabetic activity with a standard drug acarbose. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. High surface area graphene-supported metal chalcogenide assembly

    DOEpatents

    Worsley, Marcus A.; Kuntz, Joshua; Orme, Christine A.

    2016-04-19

    A composition comprising at least one graphene-supported assembly, which comprises a three-dimensional network of graphene sheets crosslinked by covalent carbon bonds, and at least one metal chalcogenide compound disposed on said graphene sheets, wherein the chalcogen of said metal chalcogenide compound is selected from S, Se and Te. Also disclosed are methods for making and using the graphene-supported assembly, including graphene-supported MoS.sub.2. Monoliths with high surface area and conductivity can be achieved. Lower operating temperatures in some applications can be achieved. Pore size and volume can be tuned.

  15. 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.

  16. Comparison of different substrates for laser-induced electron transfer desorption/ionization of metal complexes

    NASA Astrophysics Data System (ADS)

    Grechnikov, A. A.; Georgieva, V. B.; Donkov, N.; Borodkov, A. S.; Pento, A. V.; Raicheva, Z. G.; Yordanov, Tc A.

    2016-03-01

    Four different substrates, namely, graphite, tungsten, amorphous silicon (α-Si) and titanium dioxide (TiO2) films, were compared in view of the laser-induced electron transfer desorption/ionization (LETDI) of metal coordination complexes. A rhenium complex with 8-mercaptoquinoline, a copper complex with diphenylthiocarbazone and chlorophyll A were studied as the test analytes. The dependencies of the ion yield and the surface temperature on the incident radiation fluence were investigated experimentally and theoretically. The temperature was estimated using the numerical solution of a one-dimensional heat conduction problem with a heat source distributed in time and space. It was found that at the same temperature, the ion yield from the different substrates varies in the range of three orders of magnitude. The direct comparison of all studied substrates revealed that LETDI from the TiO2 and α-Si films offer a better choice for producing molecular ions of metal coordination complexes.

  17. An unsupported metal hydroxide for the design of molecular μ-oxo bridged heterobimetallic complexes.

    PubMed

    Falzone, A J; Nguyen, J; Weare, W W; Sommer, R D; Boyle, P D

    2014-02-28

    A terminal and unsupported chromium(III) hydroxide is reported. The terminal hydroxide is used to synthesize the first example of a heterobimetallic Ti-O-Cr compound containing an unsupported μ-oxo bridge. The heterobimetallic complex exhibits a new absorbance at 288 nm (4.32 eV), which is assigned to a metal-to-metal charge transfer (MMCT) transition.

  18. Surrogate models for sheet metal stamping problem based on the combination of proper orthogonal decomposition and radial basis function

    NASA Astrophysics Data System (ADS)

    Dang, Van Tuan; Lafon, Pascal; Labergere, Carl

    2017-10-01

    In this work, a combination of Proper Orthogonal Decomposition (POD) and Radial Basis Function (RBF) is proposed to build a surrogate model based on the Benchmark Springback 3D bending from the Numisheet2011 congress. The influence of the two design parameters, the geometrical parameter of the die radius and the process parameter of the blank holder force, on the springback of the sheet after a stamping operation is analyzed. The classical Design of Experience (DoE) uses Full Factorial to design the parameter space with sample points as input data for finite element method (FEM) numerical simulation of the sheet metal stamping process. The basic idea is to consider the design parameters as additional dimensions for the solution of the displacement fields. The order of the resultant high-fidelity model is reduced through the use of POD method which performs model space reduction and results in the basis functions of the low order model. Specifically, the snapshot method is used in our work, in which the basis functions is derived from snapshot deviation of the matrix of the final displacements fields of the FEM numerical simulation. The obtained basis functions are then used to determine the POD coefficients and RBF is used for the interpolation of these POD coefficients over the parameter space. Finally, the presented POD-RBF approach which is used for shape optimization can be performed with high accuracy.

  19. Adsorptive removal and separation of chemicals with metal-organic frameworks: Contribution of π-complexation.

    PubMed

    Khan, Nazmul Abedin; Jhung, Sung Hwa

    2017-03-05

    Efficient removal and separation of chemicals from the environment has become a vital issue from a biological and environmental point of view. Currently, adsorptive removal/separation is one of the most promising approaches for cleaning purposes. Selective adsorption/removal of various sulfur- and nitrogen-containing compounds, olefins, and π-electron-rich gases via π-complex formation between an adsorbent and adsorbate molecules is very competitive. Porous metal-organic framework (MOF) materials are very promising in the adsorption/separation of various liquids and gases owing to their distinct characteristics. This review summarizes the literature on the adsorptive removal/separation of various π-electron-rich compounds mainly from fuel and gases using MOF materials containing metal ions that are active for π-complexation. Details of the π-complexation, including mechanism, pros/cons, applications, and efficient ways to form the complex, are discussed systematically. For in-depth understanding, molecular orbital calculations regarding charge transfer between the π-complexing species are also explained in a separate section. From this review, readers will gain an understanding of π-complexation for adsorption and separation, especially with MOFs, to develop new insight for future research. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Design, spectral characterization and biological studies of transition metal(II) complexes with triazole Schiff bases

    NASA Astrophysics Data System (ADS)

    Hanif, Muhammad; Chohan, Zahid H.

    2013-03-01

    A new series of three biologically active triazole derived Schiff base ligands L1-L3 have been synthesized in equimolar reaction of 3-amino-1H-1,2,4-triazole with pyrrol-2-carboxaldehyde, 4-bromo-thiophene-2-carboxaldehyde, and 5-iodo-2-hydroxy benzaldehyde. The prepared Schiff bases were used for further complex formation reaction with different metal elements like Co(II), Ni(II), Cu(II) and Zn(II) as chlorides by using a molar ratio of ligand:metal as 2:1. The structure and bonding nature of all the compounds were identified by their physical, spectral and analytical data. All the metal(II) complexes possessed an octahedral geometry except the Cu(II) complexes which showed a distorted octahedral geometry. All the synthesized compounds, were studied for their in vitro antibacterial, and antifungal activities, against four Gram-negative (Escherichia coli, Shigella sonnei, Pseudomonas aeruginosa and Salmonella typhi) and two Gram-positive (Bacillus subtilis and Staphylococcus aureus) bacterial strains and against six fungal strains (Trichophyton longifusus, Candida albicans, Aspergillus flavus, Microsporum canis, Fusarium solani and Candida glabrata) by using agar-well diffusion method. It has been shown that all the synthesized compounds showed moderate to significant antibacterial activity against one or more bacterial strains. In vitro Brine Shrimp bioassay was also carried out to investigate the cytotoxic properties of these compounds. The data also revealed that the metal complexes showed better activity than the ligands due to chelation/coordination.