The topic of climate protection and, for example, the resulting need for a reduction in the use of fossil fuels, is a major focus of research. Particular interest is taken in the substitution of traditional metals such as steel with lightweight materials like aluminium and magnesium alloys in the automotive and generally in the transportation sector. Due to the hexagonal crystal structure of magnesium, the processing of its alloys contains some almost unique challenges. By alloying calcium, for example in ZAX-alloys – containing zinc, aluminium and calcium – the formability at room temperature is improved through a less pronounced texture with a basal pole split. [2] To join the replaced components in the cars, welding can be used. This process profits from procedure where base and weld material are of similar compositions. For welding, and for wire-based additive manufacturing too, wires with a diameter of approximately 1 – 1.6 mm are required, which can only be produced through drawing. The production for the preliminary products can be achieved through either extrusion or groove rolling. For the latter there is a lack of fundamental empirical experience and research results that are required for a successful application and implementation in the industry. The extrusion process is more established but groove rolling has the potential to produce larger quantities in the same time and has the added advantage of a greater grain refinement.

M.S.

The purpose of this investigation was to determine the corrosion-resistant properties of commercial magnesium-alloy tubing as compared to the corrosion resistance offered by silicone-coated magnesium-alloy, aluminum, monel and stainless steel when used as heat exchanger tubes. Two single pass, double pipe heat exchangers were constructed using pyrex glass tubes as outer shells. The pyrex tubes were two inches inside diameter, 2.25 inches outside diameter, five feet long and had flared ends. Each end of the pyrex tubes was equipped with a flange containing a 0.876 inch packing gland and a 0.75 inch inlet, or outlet port. The corrosion test tubing could be easily inserted into or removed from the packing glands without damaging the surface of the test specimen. A series of corrosion tests was made in the heat exchangers using magnesium-alloy, FS-1; silicone-coated magnesium-alloy, FS-1; aluminum, 3S; stainless steel, type 316; and monel as heat exchanger tubes. Three and ten per cent by weight sodium chloride solutions, and sulfur-bearing Texas fuel oil were used as corrosive mediums. The unit was operated at an average inlet temperature of 38 ± 1°C and an average outlet temperature of 50 ± 5°C for the sodium chloride solutions, and an average inlet temperature of 83 ± 3°C and an average outlet temperature of 94 ± 6°C for the sulfur-bearing fuel oil. Seventy-two-hour tests were made maintaining an average rate of flow of corrosive medium through the heat exchangers of 6.7 ± 0.2 gallons per minute for the sulfur-bearing fuel oil. Upon completion of the tests, the heat exchanger tubes were chemically cleaned of corrosion products. From the known weight losses, area and density of test specimens, and duration of tests, the corrosion rates were calculated. Corrosion rates expressed in inches penetration per year, due to the action of three per cent by weight sodium chloride was as listed in the following descending order: magnesium-alloy, FS-1, pitted, no calculations made; silicone-coated magnesium-alloy, FS-1, 0.1388; aluminum, 3S, 0.0508; monel, 0.0050; and stainless steel, type 316, 0.0013. Corrosion, expressed in inches penetration per year, due to action of ten per cent by weight sodium chloride was as follows: magnesium-alloy, FS-1, and silicone-coated magnesium-alloy, FS-1, pitted, no calculations made; aluminum, 3S, 0.0588; monel, 0.0071; stainless steel, type 316, 0.0036. Corrosion, expressed in inches penetration per year, due to action of sulfur-bearing fuel oil was as follows: silicone-coated magnesium-alloy, FS-1, 1.160; magnesium-alloy, FS-1, 0.897; aluminum, 3S, 0.0361; monel, 0.0095; stainless steel, type 316, 0.0029. <i>Note: After completion of this thesis, an investigation by John T. Castles concerning the use of silicone coating on steel evaporator tubes indicated that the coating contained minute holes and therefore was not impervious. These holes could have formed at points of weakness and starting points for disintegration of the silicone coating. It is recommended that the metal surface be treated prior to spraying in an attempt to obtain an impervious silicone coating. The metal surface should be thoroughly dried to insure against moisture remaining in nonconformities which would establish points of weakness under the coating. Some test should be devised which would indicate whether or not a coating was impervious.</i> / Master of Science

Magnesium and its alloys are considered as the potential biomaterials due to their biocompatibility and biodegradable characteristics but suffer from poor corrosion performance. Various surface modification techniques are employed to improve their corrosion resistance. In present case, laser surface melting was carried out on AZ31B Mg alloy with various laser energy densities using a continuous wave ytterbium laser. Effect of laser treatment on phase and microstructure evolution was evaluated by X ray diffraction and scanning electron microscopy. Multi-physics thermal model predicted time temperature evolution along the depth of the laser treatment zone. Additionally, electrochemical method and bio-immersion test were employed to evaluate the corrosion behavior in simulated body fluid medium. Microstructure revealed grain refinement and even distribution of Mg17Al12 phase along the grain boundary for laser treated samples leading to substantial enhancement in the corrosion resistance of the laser treated samples compared to the untreated alloy. The laser processed samples also possessed a superior wettability in SBF solution than the untreated sample. This was further reflected in enhanced bio-integration behavior of laser processed samples. By changing the parameters of laser processing such as power, scanning speed, and fill spacing, a controllable corrosion resistance and bioactivity/biocompatibility of the implant material was achieved.

Mg-alloys, despite being the lightest structural metallic materials, find limited applications due to their poor workability, which is due to the hcp structure that does not provide sufficient number of independent slip systems for compatible deformation. Workability improves with the increase in the deformation temperature, when non-basal slip starts playing a larger role in deformation. Efforts were made to improve the workability through control of texture, grain refinement and alloying. Alloying activates non-basal slip by decreasing the critical resolved shear stress (CRSS) on non-basal planes or by promoting cross slip through an increase in the stacking fault energy (SFE) on basal planes. In this thesis, the effect of Li addition to the most widely used wrought Mg-alloy AZ31 on its workability is examined. Plastic deformation behaviour of a series of AZ31-Li alloys with temperature, T, and strain rates, ε , as variables was studied, so as to identify the optimum Li content that results in highly workable alloy. The T and ε combinations that are best suited for hot deformation of these alloys were also identified through processing maps and microstructural analysis. First, deformation behaviour of the base AZ31 is examined in detail. Compression tests were carried out, with T ranging between 150 and 400 °C and at ranging from 10-3 to 102 s-1, covering entire hot working range of the alloy. The results suggest that the deformation behaviour of AZ31 could be partitioned into three temperature regimes. In low T regime, twinning played an important role. It changes the orientation and increases hardening rate, θ (given by dσ/dε where σ and ε are true stress and strain respectively); material exhibits macroscopic flow localization and cracking along twin boundaries. The onset of twinning was examined in detail by examining the local maxima before ϵpeak strain in plot between d2σ/dε2 vs. ε. Twinning was found to occur at all the deformation conditions. Dynamic recrystallization (DRX) was observed at temperatures above 250 °C whereas deformation at low T (< 250 °C) led to extensive twinning at all . ε . At intermediate T of 250-300 °C, plastic strains tend to localize near grain/twin boundaries, confining DRX only to these regions. Increase in T promotes non-basal slip, which, in turn, leads to uniform deformation; DRX too becomes uniform. The dependence of critical stress (σc) for the onset of DRX and peak flow stress (σp) on Zener-Hollomon parameter (Z) indicates that these stresses increase with Z. Activation energy (Q) for the deformation of AZ31 was estimated at peak stress and steady state conditions. High values of Q (150-200 kJ/mol) indicate cross slip as the rate controlling mechanism, at the peak, in the stress-strain responses. For steady state, Q corresponds to lattice/grain boundary diffusion (90-150 kJ/mol). Next, the effect of Li on deformation behaviour of AZ31 was examined. In addition to AZ31 without any Li (0Li), three alloys 1 (1Li), 3 (3Li) and 5 (5Li) wt% Li were prepared with the aid of a specially designed set-up for melting and casting of Li containing alloys. Experimental results on homogenized alloys show that 1Li alloy’s overall response is similar to that of 0Li alloy, but 3Li and 5Li alloys exhibit distinctly different deformation behaviour. Li addition facilitates cross slip by increasing SFE on basal planes, thus leading to change in the deformation mechanism of the alloy. Increased softening due to cross slip decreases θ and also the twin density at low ϵ (<10-2 s-1). During deformation at low ϵ and low T, high Li alloys reveal cavities along the grain boundaries in contrast to cracking along twin boundaries that was observed in AZ31. In the intermediate T range, high Li alloys reveal the presence of a small mantle, which can be attributed to the increased cross slip with increasing Li. In fact, Li addition was found to restrict DRX and promote dynamic recovery (DRY). As ϵ increases in this T regime deformation becomes more homogeneous and twinning occurs extensively in high Li alloys. This results in remarkable increase in dσ/dε (θ) in these alloys and DRX was predominantly seen at twinned regions. At high ϵ -T regime, where non-basal slip and twinning occur uniformly, DRX is observed throughout the samples. On the basis of d2σ/dε2 – ε plots, it was found that twinning occurs at almost all -T combinations examined in present study for 0Li and 1Li alloys. In high Li alloys, twinning activity was found to be insignificant at low ε , resulting in low twin density than low Li alloys. Twinning occurs at very early stages of deformation. In the low T and high ε regime, extensive twinning in high Li alloys is noted. In high T regime, presence of twins was not prominent due to the preferential occurrence of DRX at twin boundaries. Estimated values of Q in high Li alloys were found to be very low and correspond to lattice/grain boundary diffusion of Li in Mg, indicating that cross slip is no longer the rate controlling mechanism. Instead, unpinning of kinks from Li atoms appears to control the deformation. Cross slip is promoted by Li through increase in SFE at basal planes. Onset of the DRX was predicted and it was observed that high Li alloys posses lower σc at low ε , but at high ε , σc was either comparable to or higher than low Li alloys. Processing maps were generated for all the alloys using Prasad's as well as Murty's models. Instability predictions of Prasad’s and Murty’s models are similar, except that isoefficiency contours in the latter are slightly shifted to higher ε . These maps indicate to an increase in the workability with the addition of Li to AZ31. Instability predicted by processing maps in the low ε regime in high Li alloys is attributed to underestimation of stress values due to spline interpolation. High sensitivity observed for high Li alloy at intermediate ε (10-1 – 100 s-1) is attributed to the change in the deformation mode i.e. from slip to twinning. Deformation at high T leads to dissolution of Li containing precipitates, which in turn increases the solid solution strengthening in the alloy. Hence, increase in flow stress is observed with increase in T in high Li alloys. This structural change too causes instability predictions in the high -T regime. The 0 Li alloy exhibits peak efficiency of 45% in T = 250-400 °C and ε = 10-1.25 - 100.25 s-1 regime. DRX is observed in this regime and optimum conditions for deformation predicted for this alloys are T = 350 °C and ε = 10-1 s-1. These alloys can be worked at low ε regime too (T = 250-400 °C and ε = 10-2.5 – 10-1 s-1) where the softening mechanism is DRY. Accordingly, it is concluded that the intrinsic workability of AZ31Mg-alloy increases with the addition of 3% and 5% Li.

Abstract not available

published_or_final_version / Orthopaedics and Traumatology / Master / Master of Philosophy

The hot forming-quenching (HFQ) process has introduced grains and subgrain growth, accompanied with modification of the intermetallic particle distribution in AZ31 magnesium alloys. Each region of the HFQ component represents significant grain structure variation and surface conditions that contributed to the corrosion susceptibility. The homogeneous grain structure significantly ruled the corrosion propagation features by filiform-like corrosion. Immersion of AZ31 alloys in 3.5 wt.% NaCl indicated higher corrosion rate of HFQ TRC (corrosion rate: 10.129 mm/year), a factor of 10 times, higher than the rolled alloy (corrosion rate: 0.853 mm/year) and a factor of 2 times, higher than the corrosion rate of MCTRC alloy (corrosion rate: 5.956 mm/year). Much lower corrosion rate was indicated in the as-cast TRC and MCTRC alloys, compared to the alloys after HFQ process that revealed the contribution of network or continuous distribution of β-Mg17Al12 phase particles to reduce the corrosion driven in chloride solution. In contrast, discontinuous distribution of cathodic β-Mg17Al12 phase particles increases the corrosion rate of HFQ TRC alloy by promoting the cathodic reaction and intense filament propagation resembling the coarse interdendritic and grain boundaries attack. The presence of high population densities of cathodic Al8Mn5 particles in HFQ rolled AZ31B-H24 alloy significantly reduced the corrosion driven for intense corrosion attack on the rolled alloy. The surface preparation by mechanical grinding process induced MgO and Zn-enrichment layer, accompanied with near surface deformed layer that consisted of nanograins in the range size of 40 to 250 nm. The grinding process refined the surface by removing the cutting damage and marks that formed during the thermomechanical process and led to stable potential of the HFQ AZ31 alloys, in the range of -1.59 to -1.57 V, during open circuit potential (OCP) measurement. The surface regularity with grinding path causing the filament to propagate following the grinding direction. The as-received surface contained many cutting damages and deep scratch marks from the rolling and casting processes that could introduce many corrosion initiation sites. The absence of the grinding direction on the as-received surface could control intense corrosion susceptibility, due to the non-linear filament propagation. The surface irregularity on chromic acid cleaned surface of HFQ rolled AZ31B-H24 alloy also contributed to low corrosion potential of the rolled alloy during OCP and potentiodynamic polarization measurement.

Thesis (M.S.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 1980. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Includes bibliographical references. / by Jocelyn Irene Petit. / M.S.

Thesis (Ph. D. (Physics)) -- University of Limpopo, 2013 / A combination of ball milling experiments and ab initio calculations in this study successfully yielded results that shed light into understanding the fundamental basis for immiscibility and the concept of mechanical alloying in Ti-Mg system. In addition, the conditions for achieving extended solid solubility in elements that usually do not dissolve in each other under thermodynamic equilibrium conditions have been predicted using ultrasoft (US) and norm-conserving (NC) pseudopotentials. Hydostatic pressures required to stabilize ordered phases were determined. Our new systematic representation of martensitic transformation (MT) paths as a result of dislocation necessary to induce α→FCC, α→BCC and α→ω phase transitions led to, for the first time, a direct determination of CRSS and tensile strength for Ti and Mg HCP metals. Furthermore, a new ω phase which is less stable than α phase at 0 GPa is proposed. Based on this phase, α→ω deformation path which yielded the onset of uniaxial transition pressure of 4.167 GPa is reported. Attempts of synthesizing Ti-Mg solid solutions by means of Simoloyer high energy ball mill were not successful; however, nanocrystalline Mg-TiH2-x composites were instead formed. These results were attributed to quick formation of metastable Ti hydrides or cold welding at early stages of BM prior to alloying, thus serving as possible obstacles to forming such solid solutions. The deformed Ti crystals adsorbed H+ from the stearic acid leading to formation of metastable orthorhombic TiH2-x phase which later transformed to a tetragonal TiH2-x or even cubic TiH2 when stoichiometric amount of H2 had been adsorbed. Although the yield was significantly lower, the product of milling a mixture of coarse Mg and fine Ti particles was comprised of Ti particles adhering around ductile Mg particles in a core shell manner. The adhesion of the fine hard titanium particles on the surface of the large ductile magnesium particles impeded the further plastic deformation of the titanium particles, thus suppressing the formation of the faults necessary for mechanical alloying. Nanocrystalline Ti powder of about 40 nm was produced by 30h ball milling. During BM of Ti powder, solid-state transformation from HCP to FCC occurred in the presence of PCA with lattice parameters of 4.242 and 4.240 Å after 24 and 30 h, respectively, v due to protonation. When Ti powder was milled in the absence of PCA, no phase transformation was observed for both uninterrupted and interrupted milling cycles. In addition, nanocrystalline Mg powder with crystallite size varying between 60 and below 40 nm was produced by ball milling. However, no solid-state transformation took place even if the powder was milled for 90 h. Therefore, we evidently report for the first time that the interstitial H+ is the driving force for α → FCC phase transformation in ball milled Ti powder. Our theoretical results predicted the ω phase to be the ground-state structure of Ti at 0K and P=0 GPa, in support of other previously reported calculations. We noticed that the stability of the α phase was surpassed by that of the FCC lattice at ~ 100 GPa, corresponding with sudden sharp rise in c/a ratio, hence attributed to α → FCC phase transition. Similar results were obtained for Mg at 50 GPa, although in this case the crossing of lattice energies coincided with minimum c/a. However, using our proposed HCP→BCC MT path mechanism for Mg, it is evident that the minimum c/a at 50 GPa corresponds to a change in the preferred deformation slip from basal (below 10 GPa) to prismatic rather than phase transition. Nonetheless, the proposed MT model predicts that both elemental Ti and Mg prefer to deform via prismatic slip as indicated by lower shear stress as well as CRSS values compared to those calculated for basal slip. Theoretical findings from ab initio calculations on hypothetical ordered Ti-Mg phases indicated absence of intermetallic phases at equilibrium conditions, in agreement with experimental data. However, the formation becomes possible at 80 GPa and above with respect to c/a ratio but requires at least 200 GPa with respect to stable lattices. Using calculated heats of formation, elasticity and DOS, it has been possible to show that L12 TiMg3 could not form even at high pressure as 250 GPa. Nonetheless, both approaches indicate that forming an intermetallic compound between Ti and Mg requires a crystal structure change, α→FCC for Ti and HCP→BCC for Mg. Proposed DFT-based solid solution model for predicting phase stability and elastic properties of binary random alloys, with Mg-Li system serving as a test case, successfully yielded reliable results comparable to experimental data. This method was successfully applied to study an immiscible Ti-Mg system and the solubility limit vi was for the first time theoretically established. Based on formation energy of Ti-Mg solid solutions, our calculations predicted for the first time that the solubility of up to 60 and 100 at.% Mg into Ti with the use of USP and NCP, respectively, to be thermodynamically favourable with necessary lattice kinetics being the main challenge. Nonetheless, NCP proved to be reliable in predicting structural and elastic properties of disordered alloys.