No description available.

The extent to which dissolved Li2CO3 can inhibit corrosion of lightweight Mg alloy sheet metal in contact with aqueous NaCl solutions was determined. Two Mg alloy sheet metal alloys were studied, which include: AZ31B (3% Al, 1% Zn, 0.5% Mn, balance Mg) and ZEK100 (1.3% Zn, 0.2% Nd, 0.25% Zr, balance Mg). Corrosion inhibition was first determined for each alloy separately when immersed in 0.1 M NaCl (aq), with and without dissolved Li2CO3 added. The addition of 100 mM Li2CO3 (aq) reduces the corrosion rate of AZ31B by a factor of ~10 and ZEK100 by a factor of ~12. Inhibition involves a reduction in both global anodic dissolution and cathode (H2 gas evolution) kinetics. It also involves suppression of localized filament-like corrosion and associated anode/cathode activation. Site specific cross-sectional analysis of the surface film formed during forced anode activation (polarization) revealed the formation of a Li-doped MgO film, akin to what forms, and provides protection to, Mg alloys with Li added as an alloying element. Such film formation was used to explain all corrosion inhibition aspects. Corrosion inhibition was then determined for ZEK100 when immersed in 0.1 M NaCl (aq) with and without a spray-deposited Li2CO3 surface coatings added. A commercial hexafluoro-titanate/zirconate-polymer conversion coating (Bonderite® MNT 5200) also served as the comparative basis. The Li2CO3-coated surface exhibits the lowest relative corrosion, whereas the conversion-coated surface exhibits the highest. Improved corrosion control is attributed to the formation of a compact coating (physical contribution) and the ability of dissolved Li2CO3 to inhibit both the anode and cathode kinetics (electrochemical) contribution. The findings are of interest to automotive industry as a possible means to effectively control corrosion of Mg alloy sheet metal using Li2CO3 as a surface pre-treatment or the inclusion of Li2CO3 to a polymer as an inhibitor additive. / Thesis / Doctor of Philosophy (PhD) / The objective of this research was to determine the extent to which dissolved lithium carbonate (Li2CO3) can inhibit corrosion of lightweight magnesium (Mg) alloy sheet metal in contact with aqueous NaCl solutions. Corrosion inhibition by dissolved Li2CO3 in 0.1 M NaCl (aq) was demonstrated for two Mg alloy sheet metal alloys: AZ31B (3% Al, 1% Zn, 0.5% Mn, balance Mg) and ZEK100 (1.3% Zn, 0.2% Nd, 0.25% Zr, balance Mg). As a next step towards the development of a protective coating scheme, corrosion inhibition of ZEK100 by Li2CO3, as a surface coating applied, is achieved through a reduction of both the anodic dissolution and the cathode (H2 gas evolution) kinetics in large part by the formation of a Li-doped MgO film at anodic dissolution sites.

No description available.

The industrial practice of grain refinement of aluminium alloys involves the addition of inoculant particles to initiate alpha-aluminium grains at small undercoolings. This results in a uniformly fine, equiaxed as-cast microstructure and is commonly achieved using Al-Ti-B additions. The phase responsible for initiation of grains in aluminium melts inoculated with Al-Ti-B was determined during the 1990s; since that time, scientific understanding of grain refinement has advanced rapidly. However, one of the main problems of addition inoculants is impurities which is added to the melt and may affect the desired characteristics of the product. With regards to this problem other methods of refinement and the mechanisms of refining have not been fully understood and prediction of as-cast Microstructures in aluminium alloys has much scope for improvement. In this thesis: 1-Factors in establishing equiaxed microstructure were analysed and the origin of equiaxed grains were explored. Then the nucleation process and the involved mechanisms were investigated in depth and control of nucleation process to achieve a fine and uniform structure was set as target. 2-Refinement of microstructure with introduction of shearing was evaluated and the process of refinement in the mushy zone (semisolid state) as a base line was established. Then introduction of shearing above liquidus as a development was analysed and outstanding refinement was seen with shearing above liquidus which have not been investigated properly elsewhere. 3- The mechanisms of refinement by introducing shearing were investigated and the refining mechanisms below and specifically above liquidus were investigated systematically. As results an appropriate understanding about the mechanisms of nucleation and refinement above liquidus was established. 4- Finally, with simulation the most dominant factor in approaching fine grain size by applying shear was identified and the results of experimental examination was verified by simulation.

In this study, Mg, Sn, Cd, Bi and Sb containing, five binary, three ternary and two quaternary different alloys to be used in a Valve-Regulated Lead-Acid (VRLA) batteries have been studied in terms of their mechanical and electrochemical properties. The investigated properties are hardness, passivity, corrosion rate, hydrogen gassing and the conductivity of the passive film. All electrochemical tests were carried out in 3.75 M H2SO4 solution by using open-circuit potential, anodic polarization, polarization resistance measurement and gas collection techniques. The results showed that while the minimum hardness values were observed in Pb and Pb-Bi alloy, Mg containing alloys have the highest hardness values among all alloys. According to corrosion measurements, lowest icritical value was obtained for Pb, Pb-Bi and Pb-Sn, which reached to passivation region earlier than others. Passive film formation was seen for all specimens. The noble Ecorr value and minimum corrosion rates belonged to Pb and Pb-Mg. Pb-Bi and Pb-Cd have the highest gas evolution rate. Besides, there were not seen much difference in the gassing behavior of Pb-Sn and Pb-Sb alloys. Mg is found to have a superior effect on hydrogen gassing. Addition of Sn, as an alloying element, to lead increases the conductivity of the passivation layer. Mg containing alloys did not show good conductivity characteristic. As a result, Mg containing alloy seemed to have an important role because of the desired hardness, corrosion and, gas evolution behavior. However, conductivity of passivation layer of these alloys came up to be low due to the higher tendency of Mg to oxidation. Even so, Mg seems to be a promising alloying element for lead grid alloys in Valve-Regulated Lead-Acid (VRLA) batteries.

Název práce: Studium defekt· v kvazikrystalech Autor: Marián Vlček Katedra: Katedra fyziky nízkých teplot Vedoucí disertační práce: doc. Mgr. Jakub ížek, Ph.D., Katedra fyziky nízkých teplot Abstrakt: V predloženej práci boli pomocou spektroskopie doby života poz- itrónov a koincidenčnej spektroskopie Dopplerovského rozšírenia anihilačného píku študované zliatiny WE43 s prídavkom zinku a ternárne zliatiny Mg-Zn-Y. V týchto zliatinách bola nedávno zistená prítomnos' ikosahedrálnej fázy Mg3Zn6Y1 s kvázikryštalickou štruktúrou, čo pritiahlo pozornos' výskumníkov. Spektroskopia doby života pozitrónov preukázala prítomnos' unikátnych vakanciám podobných defektov na rozhraní ikosahedrálnej fázy a horčíkovej matrice, ktoré sú charakter- istické pre horčíkové zliatiny obsahujúce ikosahedrálnu fázu. Tepelné spracovanie skúmaných zliatin vedie k významným zmenám morfológie hraničných fáz. Ke¤že vakanciám podobné defekty spojené s ikosahedrálnou fázou sa vyskytujú na jej rozhraní s horčíkovou matricou, zmeny v morfológii ikosahedrálnej fázy vedú k výrazným zmenám koncentrácie týchto defektov. "alej boli skúmané vzorky pripravené uhlovým pretláčaním kanálom rovnakého prierezu. Typy defektov prítomné v týchto zliatinách a ich teplotná stabilita bola určená pomocou spektroskopie doby života pozitrónov a merania tvrdosti...

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23195号 / 工博第4839号 / 新制||工||1756(附属図書館) / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 辻 伸泰, 教授 奥田 浩司, 教授 安田 秀幸 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Ball milling has been shown to produce nanostructures in metal powders through severe repetitive deformation. Ball milling at cryogenic temperatures (cryomilling) is more effective in this capacity due to the low temperature by slowing recovery and minimizing diffusion distances between different components. Nanostructured metals are of interest because of their unique physical and mechanical properties. The result of cryomilling is powder consisting of crystallites on the order of 30 – 50 nm. In order to characterize the properties of this material, it is often necessary to consolidate the powder, which is often difficult without causing significant grain growth. In this work, aluminum-rich and magnesium-rich alloys of varying composition are produced by cryomilling and characterized by x-ray diffraction. A novel consolidation process called high shear powder consolidation (HSPC) is used to densify as-received and as-milled powders with minimal growth. The construction of a cryomill, along with a modification for improving process yield, has provided a platform for the study of nanocrystalline metals. It has been shown that bulk nanocrystalline materials are attainable and that alloy composition influences mechanical properties. / Master of Science

Al-Mg alloys spontaneously infiltrate into porous ceramic preform in a nitrogenous atmosphere above 750 °C with Mg either pre-alloyed or introduced at the interface to initiate the process. The governing process variables are temperature, alloy composition, atmosphere and particle size of the porous preform. The present study investigates the flow kinetics of Al-Mg melts into porous Al2O3 preforms as a function of particle size of the preform from the standpoint of a physical phenomena fluid flow through a non-uniform capillary. Pressureless infiltration involves two major stages: (a) initiation associated with an incubation period and, (b) continuation where the melt infiltrates the preform. Long (~1 hr) and irreproducible incubation periods are typically observed in the Al- Mg/Al2O3 system when the samples are slowly heated in N2 atmosphere. Such lengthy periods prior to infiltration also lead to excessive Mg loss from the system. In order to accurately measure infiltration rates during the continuation stage, the incubation period was minimized by upquenching samples in air under self-sealing conditions. Interrupted experiments reveal that infiltration occurs within 5 mins. Different phenomena are expected to dictate the capillary rise kinetics through the porous ceramic post-incubation (more specifically, retard the melt movement) (a) triple-point ridging of the melt meniscus on the alumina surface (meniscus pinning) (b) interfacial reaction limited wetting and infiltration (c) pore size and distribution of the porous ceramic (d) melt (Al-Mg) / atmosphere (N2) reaction to form products inside the pore space (decrease in permeability) (e) time-dependent loss of Mg from the system (time-dependent contact angle) Some of the above phenomena viz., fluid flow inside the porous medium and chemical reaction of the melt with the reinforcement are invariably coupled in a complex manner. The contribution of each phenomenon to the kinetics of infiltration (a) and (e) was investigated separately. Triple-line ridging Al sessile drops on alumina substrate spread 4-5 orders of magnitude slower than that predicted by hydrodynamic equilibrium. The melt is pinned by ridges leading to spreading rates of 0.4-4 mm/hr in contrast to viscous drag controlled spreading rates of 1-10 mm/sec. In order to detect ridging in the Al-Mg/Al2O3 reactive couple, uniform Al2O3 capillaries were infiltrated. Experiments were conducted under sealed configuration with metal on both sides of the capillary and Mg turnings at the interface. The uniform capillary itself was placed inside an alumina preform and the assembly upquenched to 800-900 °C to minimize evaporative loss of Mg. Examination of the inner walls of the capillary after leaching away the infiltrated metal shows rough, granular features on the polycrystalline Al2O3 surface. No continuous ridges were seen. EDS of the granular phase suggested stoichiometry of spinel, MgAl2O4, formed as a result of the reaction between the melt and the capillary. From interrupted experiments the average infiltration rate inside the uniform capillary was calculated to be in the ballpark range of 2-6 µm/sec (which is a lower limit to the meniscus velocity), an order of magnitude faster than the spreading rates observed during triple-line ridging (0.1 – 1 µm/sec) indicating that the melt front pinning was not the operative mechanism for influencing infiltration kinetics. Pore size distribution of porous medium Additionally, infiltration was found to be faster in uniform channels (fractures in a preform, annular spaces and aligned pores in freeze-cast preforms) compared to the randomly packed bed itself. The effect of pore size on infiltration kinetics was studied by varying the particle size of the packed bed. Experiments were conducted for two systems (a) non-reactive liquid polyethylene glycol PEG 600 (b) reactive Al-Mg melts into packed alumina beds as a function of particle size and temperature. The PEG 600 / Al2O3 ‘model’ system was used to benchmark the effect of pore size and distribution of the particle bed on flow kinetics from a purely physical standpoint. Typically, a Washburn type of ‘parabolic’ kinetics was observed for the non-reactive couple and the ‘effective’ hydrodynamic radius, reff was extracted. (For a uniform capillary, reff and the physical radius of the capillary are the same). Surprisingly, the ‘Washburn’ radius was found to be 1-2 orders of magnitude smaller than the average pore size and even smaller than the minimum average pore size of the compact. The ‘Washburn’ radii for infiltration of Al-Mg melts was a further order of magnitude smaller than the corresponding values for infiltration of non-reactive PEG 600 through the same packed beds. Non-uniform capillary model To predict the infiltration kinetics through porous media, a sinusoidal capillary model was developed based on the pore size distribution. The input parameters for the model were the average pore neck size and average pore bulge size, which were extracted from the experimentally measured pore size distribution. The flow was assumed to be quasi-steady state and laminar. Hagen-Poiseuille’s equation was employed to calculate the total pressure drop, which was equated with the instantaneous pressure drop across the meniscus. The meniscus velocity within the non-uniform capillary was solved numerically based on the instantaneous pressure drop. The infiltration profile for the sinusoidal capillary displayed jumps associated rise in the narrow segments of the profile while the rise through the broad segment was considerably slow. The overall infiltration profile could be fitted by a parabolic Washburn-type equation. The ‘effective’ hydrodynamic radius of such a sinusoidal capillary was found to be 2-3 orders of magnitude smaller than the average capillary size and even smaller than the narrowest opening of the sinusoidal capillary. The overall kinetics was limited by flow through the broad segment of the profile where the capillary driving force is the lowest coupled with a large viscous retarding force due to the narrow feeding segment thereby leading to extremely slow flow rates. The calculated ‘effective’ radius of the sinusoidal capillary (reff = 0.03 µm) based on the pore size distribution of the 25-37 µm (1.4-10.8 µm) packed bed was similar to the experimentally observed ‘effective’ radius for flow in the non-reactive couple (reff = 0.06 µm) implying good agreement between experiments and modeling. The model was extended for the case of pressure infiltration of Al melts into SiC & TiC compacts reported in the literature, under conditions where chemical reactions are negligible. A good agreement to within a factor of 4 between the observed kinetics and the ones predicted by the current model is observed. In order to understand the origin of this ‘unphysical’ radius dictating capillary rise, the physics of flow through a stepped capillary was analysed. The kinetics of flow through the wide segment could be expressed by an ‘effective’ drodynamic radius r 4min based on geometrical parameters of the stepped capillary as: reff= r3max (Wetting situation) where rminand rmax are the radii of the narrow and broad segments of the capillary. The ‘effective’ radius from the above equation matched well with the numerically derived ‘effective’ radius for flow through the stepped capillary. A r 2 similar expression for flow under applied pressure was derived as: reff= min rmax (non- wetting situation) which is strictly correct for large values of applied pressure. Chemical reactions influencing infiltration kinetics: Upquenched samples (time-dependent contact angle due to Mg loss) The previous investigation of fluid flow in porous media from a purely physical standpoint reveals the dominant role of the pore size and distribution in the porous medium in controlling infiltration kinetics. This however, is accurate only if chemical factors are minimized. In case of the upquenched experiments for the Al-Mg/Al2O3 system, the ‘effective’ radius was determined to be an order of magnitude smaller than that for the PEG 600/Al2O3 couple implying additional chemical factors influencing flow kinetics in this reactive system. Experiments with Mg turnings mixed with the powder bed shows faster infiltration compared to the ones where the entire Mg was placed at the interface showing that local availability of Mg was responsible for slower infiltration kinetics. Diminishing Mg at the melt front, leads to increase of surface tension and increase in contact angle. This was modeled by incorporating a kinetics (time-dependent) contact angle into the sinusoidal capillary model developed for non-reactive infiltration. The infiltration kinetics was found to be retarded in the case of a kinetic contact angle. Thus, both flow retardation through a packed bed and time-dependent variations of contact angle due to Mg loss from the system are responsible for slow pressureless infiltration kinetics of Al-Mg melts inside Al2O3 preforms. The infiltration kinetics predicted by the sinusoidal capillary model thus defines an upper envelope to the rate of infiltration and subsequent composite formation for such a process governed by fluid flow; all other factors if present in effect, retard the kinetics further. Samples processed in N2 atmosphere (reduced permeability due to AlN formation) The more practical case of composite fabrication (PRIMEXTM process) by pressureless infiltration of Al-Mg melts in a flowing N2 containing atmosphere was also examined. The kinetics of infiltration of Al-Mg melts in a flowing N2-H2 atmosphere (pO2 ~ 10-20atm) for different particle sizes of the packed bed was investigated. A large scatter in the infiltrated heights was observed and the absolute infiltration rates could not be established. Moreover, incubation periods were seen to range from 1-2 hours for different particle sizes. Post-incubation, the infiltration kinetics for a wide range of particle sizes was found to be approximately an order of magnitude slower than that for the upquenched samples. Microstructural investigations of the etched samples revealed significant AlN formation at the start of the composite near the preform/billet interface. This reduced the cross-sectional area available for melt flow and possibly led to long incubation periods encountered in the process. AlN formation was also detected in the matrix on the particle surfaces as well as in the interior of the matrix. This reduced the permeability of the compact and increased the hydrodynamic resistance for flow through the porous compact leading to slower infiltration kinetics. Thus both AlN formation in the matrix and Mg loss from the melt retard capillary flow of the melt through the porous ceramic over and above the intrinsic hydrodynamic resistance for flow through the packed bed. Role of atmosphere on the pressureless infiltration process The role of atmosphere in promoting the pressureless infiltration process was examined by using different processing atmospheres such as vacuum, N2-H2 and Ar and combinations thereof. It is known that the pressureless infiltration of Al melts into porous Al2O3 preforms requires both N2 and a critical level of Mg in the system. Samples heated under vacuum and Ar to 900 °C under open conditions did not infiltrate. Rather these showed discoloration related to the formation of MgAl2O4 on the particle surface due to reduction of Al2O3 by Mg vapour. Moreover, samples heated in Ar upto 500 °C followed by heating up in N2-H2 till 900 °C did not infiltrate indicating irreversible changes. Interestingly enough, if the samples were heated in vacuum upto 700 °C followed by N2-H2 at 900 °C, infiltration was observed. Dewetted regions of the compact were seen too adjacent to the preform-billet interface. This indicated a minimum critical partial pressure of N2, which promotes infiltration. From an analysis of the different interfacial energies and their dependence on atmosphere, it was concluded that either an increase in the solid-vapour interfacial energy (~ 10%) or a decrease in the solid-liquid interfacial energy (~ 10%) would lead to a decrease in the contact angle, θ, by 10°, large enough to ensure wettability and infiltration in certain atmospheres. It was also established that Mg infiltrates into porous Al2O3 both in N2-H2 as well as Ar under sealed conditions. So the presence of a minimum partial pressure of N2 favouring wettability was specific to the Al-Mg/Al2O3 system. (pl see the original document for formulas)

Superplastic deformation behaviour of AZ31 magnesium alloy having initial grain sizes 8, 11 and 17μm alloy was investigated at 673 K with initial strain rates ranging from 1x10-2 to 1x10-4 s-1. Mechanical data on fine grained AZ31 alloy with grain sizes 8 and 11 μm indicated a transition in deformation mechanisms. The strain rate sensitivity, m ~ 0.5 at low strain rates and m ~ 0.2 at high strain rates which suggest GBS and dislocation slip as the corresponding deformation mechanism. For coarse grained alloy having grain size 17 μm, m < 0.4 at low strain rates and ~ 0.2 at high strain rates, suggesting dislocation slip as the deformation mechanism. A superplastic maximum elongation of ~ 475% was observed for 8 μm alloy at low rate of deformation. At high strain rates, the deformation was non-superplastic for fine and coarse grained alloys. The contribution of GBS to total strain, ξ in the low strain rate regime was evaluated to be 50 – 60%, for both low and high elongation. EBSD studies indicated the maintenance of high fraction of high angle boundaries up to true strain of ~ 0.88 and a reduction in texture intensity. These observations show GBS as the dominant deformation mechanism for fine grained alloy. At higher strain rate, ξ was estimated to be 30%. Fraction of high angle boundaries was reduced and [0001] direction of grains was found to be rotated towards the tensile direction, suggesting dislocation slip. Based on mechanical data, flow localization and cavitation studies; the failure of the material during high rates of deformation was mainly due to flow localization. Extensive cavitation along with more uniform flow at a lower strain rate regime suggests the failure due to the cavity interlinkage and coalescence. The present GBS data are consistent with the previous relevant data in fine grained Mg based alloys in the low strain rate regime. The GBS data obtained in the dislocation regime in the present study are also in agreement with that of the previous investigations in fine grained Mg alloys.