Nanofabrication with metallopolymers ‐ recent developments and future perspectives

Synthetic polymers containing metals and metal centers have experienced rapid growth in the last two decades. Metal‐containing polymers have an unprecedented role to play in modern high‐tech applications including nanomanufacturing, sensing, separation and catalysis. Advancement in synthetic strategies for macromolecules has enabled the synthesis of novel, exotic and use‐inspired metallopolymers. Using state‐of‐the‐art design strategies, it is now possible to perform targeted synthesis of macromolecules with varied complexity that contain a range of metal centers either in the backbone or in the side chains of the organic moiety. The presence of an inorganic element (metals and metal centers) in organic moieties has led to a number of new physicochemical properties while implementing novel functionality to the polymer matrix. This review covers nanotechnology influenced by distinctive features of metal‐containing macromolecular systems, particularly in developing flexible, functional materials. © 2013 Society of Chemical Industry     

Linkages among energy, agriculture and environment in rural India

The interconnections between energy, agriculture and environment in rural India are analyzed in this paper using a systems perspective. Rural areas of developing countries use biomass for fuel, fodder, fertilizer and other purposes, and it is necessary to understand the fuel-fodder–fertilizer relationships for optimal biomass allocation. The allocation is explored using a linear programming model. First, the model is validated by simulating it using data for the year 1990–1991. The model is then applied for the year 2000, and several scenarios are generated to obtain answers to various policy questions. The results show that it is necessary to increase fertilizer consumption, to increase efficiencies of cooking stoves, to improve livestock feed, and/or to decrease population growth for maximizing the revenue generated in the rural system of India. It shows that when the prices of fertilizers increase, a large increase in kerosene requirements can be expected. It also points to the necessity to increase kerosene consumption to reduce emissions (due to non-commercial fuels) and soil fertility loss. For example, the carbon dioxide emissions associated with the scenarios range from 137.50 to 62.50 million tons (in carbon equivalent terms) for the high and low cases, respectively. Correspondingly, kerosene consumption ranges from 0.18 to 15.49 kilotons (kT).     

Stress analysis & life prediction of a cryogenic rocket engine thrust chamber considering low cycle fatigue, creep and thermal ratchetting

The paper deals with stress analysis, cyclic and creep life prediction of a cryogenic rocket engine thrust chamber, being used in one of the satellite launch vehicles of ISRO. The thrust chamber is of double walled construction wherein high conductivity copper alloy is used for the inner wall and stainless steel for the outer. Regenerative cooling of the chamber is achieved by passing the fuel through rectangular coolant passages milled on outer surface of the inner wall. The inner and outer walls are bonded together by brazing at high temperature. Failure of a double walled chamber occurs due to thinning of the inner wall and bulging into the chamber due to three mechanisms viz. (i) low cycle fatigue (ii) thermal ratchetting and (iii) creep. To capture the structural behaviour of the chamber in a complete sequence of operation of the engine, axisymmetric modeling and cyclic stress analysis is carried out using the ANSYS finite element analysis software package. High temperature mechanical properties, low cycle fatigue and creep properties of copper are characterised. Results of creep tests conducted at various temperatures are utilized for evaluating creep constants of Norton secondary creep model available in ANSYS. Analysis is performed in a seven load step sequence simulating one complete hot test of the engine. Life prediction is done using the cumulative damage accumulation methodology, considering the above three damage mechanisms. Allowable number of hot runs permissible is then arrived at after assigning suitable factors of safety for each damage mode.     

Effect of Hydrogen and Magnetic Field on the Mechanical Behavior of High Strength AISI 4340 Steel

Presence of hydrogen in materials is known to affect their mechanical properties due to hydrogen embrittlement problem. Steels used in various applications are prone to be exposed to aqueous electrochemical environments, which may introduce hydrogen into the alloy. These alloys are also prone to be simultaneously exposed to magnetic field, which may affect the hydrogen embrittlement susceptibility of these alloys. Therefore, it is important to examine the effect of hydrogen and magnetic field on the mechanical behavior of iron-based alloys. In this work, the effect of hydrogen and magnetic field on the fracture behavior of high strength AISI 4340 steel was examined. Three-point bend test was used to study the fracture behavior. In all the cases, the samples tested with hydrogen charging show a drastic reduction in ductility and fracture stress values. The effect of magnetic field was seen to be negligible. The hydrogen embrittlement was characterized by a change in the fracture surface from a ductile-type fracture to a brittle cleavage-type fracture. Acoustic emission signals collected during the test corresponds to the fracture behavior.     

Electrochemical characterization of Cu dissolution and chemical mechanical polishing in ammonium hydroxide–hydrogen peroxide based slurries

Chemical mechanical polishing (CMP) of copper in ammonium hydroxide based slurry in the presence of hydrogen peroxide was investigated. The polishing trend was found to be similar to that exhibited by other slurries containing hydrogen peroxide and various complexing agents used for Cu CMP. When the hydrogen peroxide concentration is increased, the polish rate increases, reaches a maximum and then decreases. The location and the magnitude of the maximum depend on the ammonium hydroxide concentration. The dissolution of copper in the NH₄OH–hydrogen peroxide solution was probed by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) experiments. Electrical equivalent circuit (EEC) and reaction mechanism analysis (RMA) were employed to determine the mechanistic reaction pathway of Cu dissolution in NH₄OH–hydrogen peroxide system. Based on the RMA analysis, a four step catalytic mechanism with two adsorbed intermediate species is proposed.     

Abdominal tuberculosis: a presumptive diagnosis

BACKGROUND: Abdominal tuberculosis (TB) is common. But the diagnosis of abdominal TB is fraught with difficulties as it is often not possible to get a microbiological confirmation of the infection. We therefore undertook this study to highlight those pertinent clinical and laboratory features which would enable one to make a provisional diagnosis of abdominal TB early, to pave way for a trial of anti-tuberculosis chemotherapy. METHOD: This is a retrospective study of 12 patients treated for abdominal TB in our department over a period of 2 years. FINDINGS: Seven of the patients suffered from chronic diarrhoea for periods ranging from 4 weeks to 12 months. Four patients had progressive abdominal distension (ascites). The last patient came in with multiple abdominal swellings. Seven patients had clinical and biochemical features of malabsorption. Another 9 patients also had persistent pyrexia. The ascitic fluid was exudative in the 4 patients mentioned earlier. A definitive diagnosis could not be established in any of these patients. The diagnosis of abdominal TB was thus one of exclusion in these patients who showed prompt response to anti-tuberculosis therapy. CONCLUSION: Our study justifies a trial of anti-TB chemotherapy in TB endemic areas in the following clinical situations: (a) patients with chronic diarrhoea of unknown aetiology and (b) patients with exudative ascitic fluid, after all other possible causes, have been excluded. A prompt response to anti-TB therapy should be accepted as sufficient ground for the diagnosis of abdominal TB even when histopathological or microbiological confirmation of the disease is not possible. Our study reflects the experience of other workers from Third World countries.     

QoS assurances through class selection and proportional differentiation in wireless networks

Quality-of-service (QoS) in wireless ad hoc networks is adversely affected by node mobility, changing network topologies, and uncontrolled medium contention. The paper addresses the challenges in concurrently providing a wide range of end-to-end throughput and delay assurances in such networks. The proposed solution is based on the neighborhood proportional delay differentiation (NPDD) service model. With NPDD, applications achieve their desired end-to-end QoS using dynamic class selection (DCS) algorithms. With simulations in various distinct mobile network scenarios, we demonstrate the significantly better QoS assurances achieved with the proposed mechanism as compared with best effort and strict priority approaches. With game theoretic concepts, we model DCS applications in an NPDD network as selfish players in a noncooperative game. For such games, we prove for single-hop and multihop NPDD networks the existence of an equilibrium, the feasibility of an equilibrium, and the guaranteed convergence to a feasible equilibrium when one exists.     

Yttrium aluminum garnet powders by nitrate decomposition and nitrate–urea solution combustion reactions—a comparative study

Precursors for yttrium aluminum garnet (Y₃Al₅O₁₂—YAG) were synthesized by simple decomposition of concentrated aqueous solution of nitrates and combustion of concentrated aqueous solution of nitrates with urea on a heater. The precursor formed by the former reaction was granules of agglomerated powder while that from the latter reaction was a voluminous and porous sponge-like mass. Both precursors were ground to powders and subjected to detailed thermogravimetric–differential thermal analysis and X-ray diffraction studies. The precursor from the simple decomposition of nitrates exhibited a total loss in weight of about 18% in stages (25 to 300 °C and 300 to 600 °C) accompanied by endotherms—characterized as processes of dehydration of absorbed moisture and decomposition of residual nitrates, respectively. The as formed precursor and that heated to 820 °C were amorphous. Crystallization to YAG phase occurred from an amorphous oxide characterized by an exotherm above 820 °C with no loss of weight. The precursor from nitrate–urea combustion reaction was found to exhibit a weight loss of 2.5% accompanied by a shallow endotherm in the range of 25 to 300 °C—characterized as the process of dehydration of absorbed moisture. No further weight loss or heat effect was noticed, confirming it to be chemically pure YAG. This as formed precursor was found to be crystalline YAG. The difference in chemical composition of the precursors formed by these two reactions is attributed to the difference in the actual reaction temperatures during their formation—lower reaction temperature for the endothermic decomposition of nitrates and higher reaction temperature for the exothermic combustion associated with the formation of a bright flame. The morphology of the precursor powder formed by the former reaction exhibited only cracks while that of the precursor from the latter reaction exhibited pores and voids. The precursor from the former reaction was calcined at 1100 °C to form into chemically pure YAG. Zeta potential variation with pH for the aqueous suspensions of the crystalline YAG powders from both the reactions exhibited a maximum value in the range of 40 to 50 mV around a pH of 4, indicating stability of these dispersions towards coagulation at this pH. Particle size distribution of wet ground powders (slurries with 20%, v/v, solid at a pH of 4) showed that the powder from combustion reaction could be formed into a finer size than that from simple nitrate decomposition, indicating the agglomerates of combustion reaction were softer.     

Detecting vascular access dysfunction

Access flow (QACC) is a major determinant of patency. Access recirculation (AR > 2%), normalized venous intra-access pressure (vPIA/MAP), and QACC are used to detect access dysfunction. We compared these three measures of access function (ultrasound dilution to measure AR and QACC). A total of 779 measurements were performed on 58 arteriovenous fistulas (AVFs) and 114 polytetrafluoroethylene (PTFE) grafts (1-8/access) over 13 months, and the access parameters at the beginning of each period were related to access events within that period. Pump blood flow averaged > 420 ml/min. AR occurred uncommonly (3.8%), and in half the cases, resulted from technical error by staff. In accesses that thrombosed or underwent intervention for stenosis, AR was present in only 3 of 11 AVFs and 8 of 57 PTFE accesses. When AR was present in grafts, QACC averaged 270 +/- 23, and access thrombosis followed unless intervention occurred. In grafts, vPIA/MAP averaged 0.34 +/- 0.01 in those remaining patent, 0.52 +/- 0.08 in those that had undergone intervention, and 0.54 +/- 0.04 in those that had thrombosed. QACC averaged 1,121 +/- 26, 605 +/- 45, and 550 +/- 65 ml/min, respectively, in the three groups. By contrast, QACC differed significantly in patent AVFs (1,053 +/- 35) compared with failing AVFs (363 +/- 48), but vPIA/MAP did not. AR is thus a late manifestation of access failure. QACC is the best diagnostic test of access dysfunction in AVFs. Interpretation of vPIA/MAP in grafts is enhanced by periodic QACC measurements.     

Selection of timed token protocol parameters to guarantee messagedeadlines

Networks that use the timed token protocol (such as the 100 Mbit/s FDDI network) are well suited for real-time applications because they guarantee, to each node, an average bandwidth and a bounded access time to the communication network. This guarantee is necessary but not sufficient for the timely delivery of deadline-constrained messages; protocol parameters must be carefully selected to ensure that these messages meet their deadlines. This paper addresses the issue of selecting the protocol parameters TTRT (target token rotation time) and the synchronous capacities assigned to each node. The objective is to guarantee that each synchronous message is transmitted before its deadline. An upper bound is derived on the worst case achievable utilization (WCAU) of any parameter selection scheme. The WCAU of a scheme is defined as the maximum utilization U such that the scheme guarantees all synchronous messages as long as their utilization is less than U. An algorithm for selecting the above parameters is proposed, The algorithm is shown to have a WCAU that is very close to the upper bound