Metal-Free Polymethyl Methacrylate (PMMA) Nanoparticles by Enamine "Click" Chemistry at Room Temperature

"Click" chemistry has become an efficient avenue to unimolecular polymeric nanoparticles through the self-crosslinking of individual polymer chains containing appropriate functional groups. Herein we report the synthesis of ultra-small (7 nm in size) polymethyl methacrylate (PMMA) nanoparticles (NPs) by the "metal-free" cross-linking of PMMA-precursor chains prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization containing beta-ketoester functional groups. Intramolecular collapse was performed by the one-pot reaction of beta-ketoester moieties with alkyl diamines in tetrahydrofurane at r.t. (i.e., by enamine formation). The collapsing process was followed by size exclusion chromatography and by nuclear magnetic resonance spectroscopy. The size of the resulting PMMA-NPs was determined by dynamic light scattering. Enamine "click" chemistry increases the synthetic toolbox for the efficient synthesis of metal-free, ultra-small polymeric NPs.

Fiber Bragg Gratings, IT Techniques and Strain Gauge Validation for Strain Calculation on Aged Metal Specimens

This paper studies the feasibility of calculating strains in aged F114 steel specimens with Fiber Bragg Grating (FBG) sensors and infrared thermography (IT) techniques. Two specimens have been conditioned under extreme temperature and relative humidity conditions making comparative tests of stress before and after aging using different adhesives. Moreover, a comparison has been made with IT tecniques and conventional methods for calculating stresses in F114 steel. Implementation of Structural Health Monitoring techniques on real aircraft during their life cycle requires a study of the behaviour of FBG sensors and their wiring under real conditions, before using them for a long time. To simulate aging, specimens were stored in a climate chamber at 70 degrees C and 90% RH for 60 days. This study is framed within the Structural Health Monitoring (SHM) and Non Destructuve Evaluation (NDE) research lines, integrated into the avionics area maintained by the Aeronautical Technologies Centre (CTA) and the University of the Basque Country (UPV/EHU).

Trace Metal Sensors for Coastal Monitoring, Seaside, California, April 11-13, 2005: workshop proceedings

The Alliance for Coastal Technologies (ACT) Workshop on Trace Metal Sensors for Coastal Monitoring was convened April 11-13, 2005 at the Embassy Suites in Seaside, California with partnership from Moss Landing Marine Laboratories (MLML) and the Monterey Bay Aquarium Research Institute (MBARI). Trace metals play many important roles in marine ecosystems. Due to their extreme toxicity, the effects of copper, cadmium and certain organo-metallinc compounds (such as tributyltin and methylmercury) have received much attention. Lately, the sublethal effects of metals on phytoplankton biochemistry, and in some cases the expression of neurotoxins (Domoic acid), have been shown to be important environmental forcing functions determining the composition and gene expression in some groups. More recently the role of iron in controlling phytoplankton growth has led to an understanding of trace metal limitation in coastal systems. Although metals play an important role at many different levels, few technologies exist to provide rapid assessment of metal concentrations or metal speciation in the coastal zone where metal-induced toxicity or potential stimulation of harmful algal blooms, can have major economic impacts. This workshop focused on the state of on-site and in situ trace element detection technologies, in terms of what is currently working well and what is needed to effectively inform coastal zone managers, as well as guide adaptive scientific sampling of the coastal zone. Specifically the goals of this workshop were to: 1) summarize current regional requirements and future targets for metal monitoring in freshwater, estuarine and coastal environments; 2) evaluate the current status of metal sensors and possibilities for leveraging emerging technologies for expanding detection limits and target elements; and 3) help identify critical steps needed for and limits to operational deployment of metal sensors as part of routine water quality monitoring efforts. Following a series of breakout group discussions and overview talks on metal monitoring regulatory issues, analytical techniques and market requirements, workshop participants made several recommendations for steps needed to foster development of in situ metal monitoring capacities: 1. Increase scientific and public awareness of metals of environmental and biological concern and their impacts in aquatic environments. Inform scientific and public communities regarding actual levels of trace metals in natural and perturbed systems. 2. Identify multiple use applications (e.g., industrial waste steam and drinking water quality monitoring) to support investments in metal sensor development. (pdf contains 27 pages)

Atomistic Simulation On Size-Dependent Yield Strength And Defects Evolution Of Metal Nanowires

A simple derivation based on continuum mechanics is given, which shows the surface stress is critical for yield strength at ultra-small scales. Molecular dynamics (MD) simulations with modified embedded atom method (MEAM) are employed to investigate the mechanical behaviors of single-crystalline metal nanowires under tensile loading. The calculated yield strengths increasing with the decrease of the cross-sectional area of the nanowires are in accordance with the theoretical prediction. Reorientation induced by stacking faults is observed at the nanowire edge. In addition. the mechanism of yielding is discussed in details based on the snapshots of defects evolution. The nanowires in different crystallographic orientations behave differently in stretching deformation. This study on the plastic properties of metal nanowires will be helpful to further understanding of the mechanical properties of nanomaterials. (C) 2009 Elsevier B.V. All rights reserved.

Determination Of Interfacial Properties Between Metal Film And Ceramic Substrate With An Adhesive Layer

Peel test measurements and inverse analysis to determine the interfacial mechanical parameters for the metal film/ceramic system are performed, considering that there exist an epoxy interface layer between film and ceramic. In the present investigation, Al films with a series of thicknesses between 20 and 250 mu m and three peel angles of 90, 135 and 180 degrees are considered. A finite element model with the cohesive zone elements is used to simulate the peel test process. The finite element results are taken as the training data of a neural network in the inverse analysis. The interfacial cohesive energy and the separation strength can be determined based on the inverse analysis and peel experimental result. (C) 2008 Elsevier Ltd. All rights reserved.

Bonding Of Alumina And Metal Using Bulk Metallic Glass Forming Alloy

Metal-alumina joints have found various practical applications in electronic devices and high technology industry. However, making of sound metal ceramic brazed couple is still a challenge in terms of its direct application in the industry. In this work we successfully braze copper with Al2O3 ceramic using Zr52.5Cu17.9Ni14.6Al10Ti5 bulk metallic glass forming alloy as filler alloy. The shear strength of the joints can reach 140 MPa, and the microstructrural analysis confirms a reliable chemical boning of the interface. The results show that the bulk metallic glass forming alloys with high concentration of active elements are prospective for using as filler alloy in metal-ceramic bonding.

Interface Fracture Behavior Of Electroplated Coating On Metal Substrate Under Compressive Strain

The inducement of interface fracture is crucial to the analysis of interfacial adhesion between coating and substrate. For electroplated coating/metal substrate adhering materials with strong adhesion, interface cracking and coating spalling are difficult to be induced by conventional methods. In this paper an improved bending test named as T-bend test was conducted on a model coating system, i.e. electroplated chromium on a steel substrate. After the test, cross-sections of the coated materials were prepared to compare the failure behaviors under tensile strain and compressive strain induced by T-bend test. And the observation results show that coating cracking, interface cracking and partial spalling appear step by step. Based on experimental results, a new method may be proposed to rank the coated materials with strong inter-facial adhesion. (C) 2008 Elsevier B.V. All rights reserved.

Synthesis, structure, and photophysics of polypyridophenazine transition-metal complexes

The condensation of phenanthroline-5,6-dione (phendione) with polyamines is a versatile synthetic route to a wide variety of chelating ligands. Condensation with 2,3- napthalene diamine gives benzo[i]dipyrido[3,2-a:2',3'-c]phenazine (bdppz) a ligand containing weakly-coupled orbitals of benzophenazine (bpz) and 2,2' -bipyridinde(bpy) character. The bpy character gives Re and Ru complexes excited-state redox properties; intramolecular electron transfer (ET) takes place to the bpz portion of the ligand. The charge-separated state so produced has an extraordinarily-long 50 µs lifetime. The slow rate of charge recombination arises from a combination of extremely weak coupling between the metal center and the bpz acceptor orbital and Marcus "inverted region" behavior. Molecular orbital calculations show that only 3% the electron density in the lowest unoccupied molecular orbital lies on the bpy atoms of bdppz, effectively trapping the transferred electron on the bpz portion. The rate of charge recombination decreases with increasing driving force, showing that these rates lie in the inverted region. Comparison of forward and back ET rates shows that donor-acceptor coupling is four orders of magnitude greater for photoinduced electron transfer than it is for thermal charge recombination.

Condensation of phendione with itself or tetramines gives a series of binucleating tetrapyridophenazine ligands of incrementally-varying coordination-site separation. When a photoredox-active metal center is attached, excited-state energy and electron transfer to an acceptor metal center at the other coordination site can be studied as a function of distance. A variety of monometallic and homo- and heterodimetallic tetrapyridophenazine complexes has been synthesized. Electro- and magnetochemistry show that no ground-state interaction exists between the metals in bimetallic complexes. Excited-state energy and electron transfer, however, takes place at rates which are invariant with increasing donor-acceptor separation, indicating that a very efficient coupling mechanism is at work. Theory and experiment have suggested that such behavior might exist in extended π-systems like those presented by these ligands.

Condensation of three equivalents of 4,5-dimethyl-1,2-phenylenediamine with hexaketocyclohexane gives the trinucleating ligand hexaazahexamethyltrinapthalene (hhtn). Attaching two photredox-active metal centers and a third catalytic center to hhtn provides means by which multielectron photocatalyzed reactions might be carried out. The coordination properties of hhtn have been examined; X-ray crystallographic structure determination shows that the ligand's constricted coordination pocket leads to distorted geometries in its mono- and dimetallic derivatives.