Effect of plasticizers on magnesium-poly(ethyleneoxide) polymer electrolyte

Solid polymer electrolytes (SPEs) of poly(ethyleneoxide) and magnesium triflate, which are plasticized with propylene carbonate (PC), ethylene carbonate (EC) and a mixture of PC and EC, are studied for their conductivity, ac impedance of the Mg I SPE interface, cyclic voltammetry, infrared spectroscopy and differential scanning calorimetry. in the presence of plasticizers, the ionic conductivity (a) increases from a value of 1 x 10(-8) S cm(-1) to about 1 x 10(-4) S cm(-1) at ambient temperature. The a is found to follow a VTF relationship with temperature. The values of the activation energy, pre-exponential factor and equilibrium glass transition temperature are shown to depend on the concentration of plasticizer. Ac impedance studies indicate lower interfacial impedance of Mg/plasticized SPE than stainless steel/plasticized SPE. The impedance spectra are analyzed using a non-linear least square curve fitting technique and the interfacial resistance of Mg/plasticized SPE is evaluated. The cyclic voltammetric results suggest a quasireversible type of Mg/Mg2+ couple in plasticized SPE. (C) 2000 Elsevier Science B.V. All rights reserved.

Role of aluminum-magnesium alloys in humid aging of composite solid propellants

The humid aging of composite propellants containing a terpolymer of polybutadiene, acrylic acid, and acrylonitrile (PBAN) as a binder has been studied as a function of aging temperature, relative humidity, and aging time. Three composite types - AP-PBAN, AP-Al-PBAN, and AP-(Al-Mg) alloy- PBAN - have been studied. The burning rates of all three propellant types were unaffected by aging. The calorimetric values of composites containing aluminum-magnesium alloy decreased on aging, and the lattice parameter of the alloy decreased to a value close to that of aluminum. Water absorption in all of the samples increased with increases in the temperature, relative humidity, and aging time. The compression strength of the nonmetalized and aluminized samples decreased on aging, whereas that of the composites containing the alloy increased. The latter effect has been traced to reaction of residual carboxyl groups on the polymer chains with magnesium, leading to cross-linking. The reaction between the -COOH groups and magnesium has been proved using infrared spectroscopy. (Author)

Creep Behaviour of AE42 Magnesium Alloy and Its Composites Using Impression Creep Technique

The creep behaviour of a creep-resistant AE42 magnesium alloy has been examined in the temperature range of 150 to 240 degrees C at the stress levels ranging from 40 to 120 MPa using impression creep technique. A normal creep behaviour, i.e., strain rate decreasing with strain and then reaching a steady state, is observed at all the temperatures and stresses employed The stress exponent varies from 5.1 to 5.7 and the apparent activation energy varies from 130 to 140 kJ/mol, which suggests the high temperature climb of dislocation controlled by lattice self-diffusion being the dominant creep mechanism in the stress and temperature range employed The creep behaviour of the AE42 alloy has also been compared with its composites reinforced with Saffil short fibres and SiC particles in four combinations. All the composites exhibited a lower creep rate than the monolithic AE42 alloy tested at the same temperature and stress levels and the decrease in creep rate was greater in the longitudinal direction than in the transverse direction, as expected. All the hybrid composites, i.e., the composites reinforced with a combination of Saffil short fibres and SiC particles, exhibited creep rates comparable to the composite reinforced with 20% Saffil short fibres alone at all the temperature and stress levels employed, which is beneficial from the commercial point of view.

Laser Surface Alloying of a Creep Resistant Magnesium Alloy MRI 230D with Al and Al2O3

A creep resistant permanent mould cast Mg alloy MRI 230D was laser surface alloyed with Al and a mixture of Al and Al2O3 using pulsed Nd:YAG laser irradiation at four different scan speeds in order to improve the corrosion and wear resistance. The microstructure, corrosion and wear behavior of the laser surface alloyed material is reported in this manuscript. The coating comprised of a featureless microstructure with cellular-dendritic microstructure near the interface and exhibited good interfacial bonding. A few solidification cracks reaching down to substrate were also observed. The two step coating with Al followed by a mixture of Al and Al2O3 exhibited a slightly better corrosion resistance than the single step coating with Al. In the long run, however, corrosion resistance of both the coatings became comparable to the as-cast alloy. The corroded surface of the laser surface alloyed specimens revealed a highly localized corrosion. The laser surface alloyed specimens exhibited an improvement in wear resistance. The laser scan speed did not exhibit a monotonic trend either in corrosion or wear resistance.

Equivalent circuit parameters of the film-covered magnesium/electrolyte interface in Mg/MnO2 dry cells from transient and ac impedance measurements

The electrochemical properties of the film-covered anode/solution interface in the magnesium/ manganese dioxide dry cell have been evaluated. The most plausible electrical equivalent circuit description of the Mg/solution interface with the passive film intact, has been identified. These results are based on the analysis of ac impedance and voltage transient measurements made on the dry cell under conditions which cause no damage to the protective passive film on the anode. The study demonstrates the complementary character of impedance and transient measurements when widely different frequency ranges are sampled in each type of investigation. The values and temperature dependence of the anode-film resistance, film capacitance, double-layer capacitance and charge-transfer resistance of the film-covered magnesium/solution interface have been determined. The magnitude of these values and its implications in understanding the important performance aspects of the magnesium/manganese dioxide dry cell are discussed. The study may be extended, in principle, to Li, Al and Ca batteries.

Equivalent circuit parameters of the film-covered magnesium/electrolyte interface in Mg/MnO2 dry cells from transient and ac impedance measurements

The electrochemical properties of the film-covered anode/solution interface in the magnesium/ manganese dioxide dry cell have been evaluated. The most plausible electrical equivalent circuit description of the Mg/solution interface with the passive film intact, has been identified. These results are based on the analysis of ac impedance and voltage transient measurements made on the dry cell under conditions which cause no damage to the protective passive film on the anode. The study demonstrates the complementary character of impedance and transient measurements when widely different frequency ranges are sampled in each type of investigation. The values and temperature dependence of the anode-film resistance, film capacitance, double-layer capacitance and charge-transfer resistance of the film-covered magnesium/solution interface have been determined. The magnitude of these values and its implications in understanding the important performance aspects of the magnesium/manganese dioxide dry cell are discussed. The study may be extended, in principle, to Li, Al and Ca batteries.

Grain Growth in ECAE Processed Pure Magnesium

Grain growth kinetics was studied for commercially pure magnesium subjected to equal channel angular extrusion (ECAE). The specimens were ECAE processed upto 4 passes at 523 K following all the three important routes, namely A, 13, and C. Texture and microstructures of the samples were studied using Electron Back Scattered Diffraction (EBSD) technique in a Field Emission Gun Scanning Electron Microscope (FEG-SEM). It was observed that the grain size significantly reduces after ECAE. ECAE process produces a slightly rotated B and C-2 fiber. Static annealing leads to normal grain growth with unimodal distribution of grains through out the temperature range. Average activation energy for grain growth in the temperature range studied is found to be less than the activation energy for lattice diffusion and grain boundary diffusion of magnesium. No significant change in texture during isochronal annealing for 1 hour i.e., the predominant deformation texture remains same.

Effect of magnesium addition and heat treatment on mild wear of hypoeutectic aluminium-silicon alloys

The effect of magnesium addition and subsequent heat treatment on mild wear of a cast hypoeutectic aluminium-silicon alloy when slid against EN 24 steel is studied. Morphology and chemistry of worn surface and subsurface are studied with a view to identify wear mechanism. Stability of an iron-aluminium mixed surface layer was found to be the key factor controlling wear resistance.

Terminal solid solubilities at 900–1000°C in the magnesium oxide-zinc oxide system measured using a magnesium fluoride solid-electrolyte galvanic cell

The terminal solid solubilities of the periclase (MgO-rich) and zincite (ZnO-rich) solid solutions in the MgO---ZnO system have been determined by measuring the activity of MgO using a solid-state galvanic cell of the type 02(g), Pt/MgO, MgF2//MgF2//{χMgO+(1-χ)ZnO}(s, sln), MgF2/Pt, O2(g) in the temperature range 900–1050°C. The ZnO activity was calculated by graphical Gibbs-Duhem integration. The activity-composition plots of both components exhibit a strong positive deviation from ideality and are characterised by a miscibility gap. The terminal solid solubilities of the periclase and zincite solid solutions obtained from the activity-composition plots are found to be in reasonable agreement with those reported in the literature.

Impedance parameters and the state-of-charge. III. Zinc-manganese dioxide and magnesium-manganese dioxide dry batteries

The problem of non-destructive determination of the state-of-charge of zinc- and magnesium-manganese dioxide dry batteries is examined experimentally from the viewpoint of internal impedance and open-circuit voltage at equilibrium. It is shown that the impedance is mainly charge-transfer controlled at relatively high states-of-charge and progressively changes over to diffusion control as the state-of-charge decreases in the case of zinc-manganese dioxide dry batteries. On the other hand, the impedance is mainly diffusion controlled for undischarged batteries but becomes charge-transfer controlled as soon as there is some discharge in the case of magnesium-manganese dioxide batteries. It is concluded that the determination of state-of-charge is not possible for both types of batteries by the measurement of impedance parameters due to film-induced fluctuations of these parameters. The measurement of open-circuit voltage at equilibrium can be used as a state-of-charge indicator for Zn-MnO2 batteries but not for Mg-MnO2 batteries.

Electrical transport in magnesium aluminate

The conductivity of MgAl2O4 has been measured at 1273, 1473 and 1673 K as a function of the partial pressure of oxygen ranging from 105 to 10−14 Pa. The MgAl2O4 pellet, sandwiched between two platinum electrodes, was equilibrated with a flowing stream of either Ar + O2, CO + CO2 or Ar + H2 + H2O mixture of known composition. The gas mixture established a known oxygen partial pressure. All measurements were made at a frequency of 1 kHz. These measurements indicate pressure independent ionic conductivity in the range 1 to 10−14 Pa at 1273 K, 10−1 to 10−12 Pa at 1473 K and 10−1 to 10−4 Pa at 1673 K. The activation energy for ionic conduction is 1·48 eV, close to that for self-diffusion of Mg2+ ion in MgAl2O4 calculated from the theoretical relation of Glyde. Using the model, the energy for cation vacancy formation and activation energy for migration are estimated.

Chronic suppression of testicular function by constant infusion of gonadotropin-releasing hormone agonist and testosterone supplementation in the bonnet monkey (Macaca radiata)

Objective: To study the efficacy of long-term buserelin acetate infusion to desensitize pituitary and block testicular function in adult male monkeys (Macaca radiata). Animals: Proven fertile male monkeys exhibiting normal testicular function. Protocol: Each of the control (n = 5) and experimental monkeys (n = 10) received a fresh miniosmotic pump every 21 days, whereas pumps in controls delivered vehicle of experimentals released 50-mu-g buserelin acetate every 24 hours. On day 170 (renewed every 60 days) a silastic capsule containing crystalline testosterone (T) was implanted in the experimental monkeys. At the end of 3 years, treatment was stopped, and recovery of testicular function and fertility monitored. Results: (1) Treatment resulted in marked reduction of nocturnal but not basal serum T; (2) the pituitary remained desensitized to buserelin acetate throughout the 3-year period; (3) animals were largely azoospermic with occasional oligospermia exhibited by two monkeys; and (4) withdrawal of treatment restored testicular function, with 70% of animals regaining fertility. Conclusion: Long-term infertility (but restorable) can be induced in male monkeys by constant infusion of buserelin acetate and T.

Processing map for hot working of as cast magnesium

The constitutive flow behaviour in hot working of as cast magnesium has been studied with the help of a processing map developed in the temperature range 300-550°C and strain rate range 0·001-100 s−1. The map, interpreted using the dynamic materials model, revealed that the material undergoes dynamic recrystallisation at 425°C and 0·3 s−1, which are the optimum parameters for hot working. Ai temperatures higher than 450°C and strain rates lower than about 0·1 s−1, wedge cracking occurs in as cast magnesium. The wedge cracking domain has a high efficiency of power dissipation (60%), whereas the dynamic recrystallisation domain has a value of 34%. At temperatures below 450°C and strain rates above 10 s−1, the material exhibits flow instability in the form of mechanical twinning. At higher temperatures and strain rates, instability is manifested by flow localisation.