<p> Intercritically annealed steels, such as dual-phase steels, have found widespread use in automotive structural components due to their high strength and ductility. Elements such as Mn, Al and Si, added to improve the mechanical properties are selectively oxidized during heat treatment and limit the ability of the alloy to be reactively wet during continuous hot-dip galvanizing. Subsequently, a limit has been placed on the amount of alloy which can be used if the steel is to be subsequently galvanized. The specifics of this limit have not been explored in detail, nor has the mechanism of decreased wettability been well demonstrated in the literature other than to say that the galvanizing reaction is limited by oxides on the surface.</p> <p> Using a force balance, it is shown that the presence of MnO on the surface of steels greatly reduces the wettability with a typical galvanizing bath (Zn-0.2wt%Al, Fe-saturated, 460°C). Furthermore, it was determined that this is caused by the additional and rate-limiting step of aluminothermic reduction of the oxide layer with the bath Al, required for subsequent inhibition layer formation. By using a low pO2 during annealing, the wettability was improved by reducing the thickness of the MnO layer when compared to intermediate and industrially common values of pO2. Using a high pO2 also resulted in improved wettability since the internal oxide which was formed did not reduce the wettability since it was not exposed to the bath alloy.</p> <p> Improvements in hardenability were also explored via dilatometry showing that the formation of bainite is delayed with increasing Mn content, as well as a decrease in transformation temperatures from γ during cooling (i.e. Ms and Bs). At ~5wt% Mn, only the the transformation to αM could be observed. This opens the door to higher strength, galvanized steels - as well as possibly galvanized martensitic steels.</p> / Thesis / Master of Applied Science (MASc)

Powder metallurgy (PM) steel is produced by near net shape manufacturing, which is used to fabricate alloy steels for many purposes. Designing new powder metal steels that can form a significant fraction of martensite relies on hardenability calculations developed for wrought steels. These proven tools are built upon assumptions for wrought steels that do not hold true for PM steels. One assumption is that the alloying elements are homogenized throughout the material. In admixed powder blends that are industrially sintered this is not the case. Using prealloyed powder is a solution to this issue, yet it places restrictions on alloy design and compressibility. There are tools available to computationally optimize diffusion problems, yet the complexity during the sintering of PM steel is such that a robust model has yet been produced. It is intuitive that with smaller particles of Fe sintering time can be reduced. A direct experimental investigation linking Fe-powders’ sizes and hardenability on Fe-C-Cr-Mn-Mo-Ni PM steel was subject to microstructure analysis and mechanical properties (Jominy test) for comparative analysis. Another assumption that is made for wrought steel is a consistent density of 7.87g/cm3. This is not the case for PM steel as the press and sinter method produces pores, decreasing the density. This directly affects the thermal conductivity and phase transformation of the steel. In an effort to understand how these differences affect Grossmann’s predictions of hardenability, a direct experimental investigation linking the density to hardenability was launched on prealloyed FL-4605 and FL-4605+2%Cu. Specifically the Jominy test was completed on a range of densities, as well as compared to software predictions. The chemical variations in admixed and sintered PM steel produce a unique system where one TTT diagram cannot predict the entire final microstructure. PM steel such as this is observed in industry, and can be created through incorporating larger Fe-particles such that less alloying constituents have a chance to fully alloy these regions. Since the large particles will not have the chance to be alloyed, they will not have the ability to form martensite. Since the regions between large particles will be alloyed, martensite will form, creating a hard matrix surrounding softer particles. This structure is characteristic of a metal matrix composite (MMC), and therefore should be treated as such. There are methods of MMC design that involve numerical methods of predicting strength and toughness. These methods, along with experimental data (tensile and Charpy testing) of Fe-C-Cr-Mn-Mo-Ni PM steels with ranging volume fractions of pearlitic inclusions were compared. / Thesis / Master of Applied Science (MASc)

High entropy alloys (HEAs) is a concept wherein alloys are constructed with five or more elements mixed in equal proportions; these are also known as multi-principle elements (MPEs) or complex concentrated alloys (CCAs). This PhD thesis dissertation presents research conducted to develop precipitation-hardenable high entropy alloys using a much-studied fcc-based equi-atomic quaternary alloy (CoCrFeNi). Minor additions of aluminium make the alloy amenable for precipitating ordered intermetallic phases in an fcc matrix. Aluminum also affects grain growth kinetics and Hall-Petch hardenability. The use of a combinatorial approach for assessing composition-microstructure-property relationships in high entropy alloys, or more broadly in complex concentrated alloys; using laser deposited compositionally graded AlxCrCuFeNi2 (0 < x < 1.5) complex concentrated alloys as a candidate system. The composition gradient has been achieved from CrCuFeNi2 to Al1.5CrCuFeNi2 over a length of ~25 mm, deposited using the laser engineered net shaping process from a blend of elemental powders. With increasing Al content, there was a gradual change from an fcc-based microstructure (including the ordered L12 phase) to a bcc-based microstructure (including the ordered B2 phase), accompanied with a progressive increase in microhardness. Based on this combinatorial assessment, two promising fcc-based precipitation strengthened systems have been identified; Al0.3CuCrFeNi2 and Al0.3CoCrFeNi, and both compositions were subsequently thermo-mechanically processed via conventional techniques. The phase stability and mechanical properties of these alloys have been investigated and will be presented. Additionally, the activation energy for grain growth as a function of Al content in these complex alloys has also been investigated. Change in fcc grain growth kinetic was studied as a function of aluminum; the apparent activation energy for grain growth increases by about three times going from Al0.1CoCrFeNi (3% Al (at%)) to Al0.3CoCrFeNi. (7% Al (at%)). Furthermore, Al addition leads to the precipitation of highly refined ordered L12 (γ′) and B2 precipitates in Al0.3CoCrFeNi. A detailed investigation of precipitation of the ordered phases in Al0.3CoCrFeNi and their thermal stability is done using atom probe tomography (APT), transmission electron microscopy (TEM) and Synchrotron X-ray in situ and ex situ analyses. The alloy strengthened via grain boundary strengthening following the Hall-Petch relationship offers a large increment of strength with small variation in grain size. Tensile strength of the Al0.3CoFeNi is increased by 50% on precipitation fine-scale γ′ precipitates. Furthermore, precipitation of bcc based ordered phase B2 in Al0.3CoCrFeNi can further strengthen the alloy. Fine-tuning the microstructure by thermo-mechanical treatments achieved a wide range of mechanical properties in the same alloy. The Al0.3CoCrFeNi HEA exhibited ultimate tensile strength (UTS) of ~250 MPa and ductility of ~65%; a UTS of ~1100 MPa and ductility of ~30%; and a UTS of 1850 MPa and a ductility of 5% after various thermo-mechanical treatments. Grain sizes, precipitates type and size scales manipulated in the alloy result in different strength ductility combinations. Henceforth, the alloy presents a fertile ground for development by grain boundary strengthening and precipitation strengthening, and offers very high activation energy of grain growth aptly suitable for high-temperature applications.

Avaliou-se experimentalmente o ferro fundido branco de alto-cromo-molibdênio ao qual foi adicionado nióbio, a respeito de sua temperabilidade. Dilatometricamente traçou-se a curva TTT desse material, bem como a de um ferro fundido branco de alto cromo para efeito comparativo. Constatou-se por essa comparação e pelos resultados da literatura a alta temperabilidade obtida pela liga experimental. A partir da temperatura de austenitização utilizada, podem-se usar taxas de resfriamento de até 0,12°C/s sem transformação de fase, enquanto que na liga comparativa essa taxa aumenta para 5,8°C/s. Foram realizadas análises de desgaste abrasivo, de dureza e microdureza, de difração por raios-X , de fase magnética e de microanálise como forma de caracterizar as transformações de fase observadas por dilatometria. As variações estruturais decorrentes dos tratamentos térmicos realizados nas duas ligas foram acompanhados por microscopia ótica. É indicativo pelo presente trabalho que tal material além de suas características inerentes de resistência à abrasão e à corrosão oferece maior flexibilidade nos projetos que envolvam paredes espessas. / In this work we studied the hardenability of high chromium- molibdenum white cast iron with niobium. By dilatometry we obtained the TTT curve of this material as well as the high chromium white cast iron for comparison. This comparison and available results in literature confirm the high temperability of experimental material. We can use slow rate cooling 0,12°C/s or higher without phase transformation, while in the comparative alloy this rate is around 5,8°C/s or higher from specific used austenitic abrasive temperature. We also realized analysis of abrasive wear, hardness and microhardness, raios-X difraction, magnetic phase and microanalyse for verifing the phase transformation as observed by dilatometry. The structure variation as function of termic treatment in both alloys is monitored by optical microscope. The present work indicate that the material under study can offer more flexibility for projects with thick materials apart from intrinsic characteristics of abrasive wear and corrosion.

Avaliou-se experimentalmente o ferro fundido branco de alto-cromo-molibdênio ao qual foi adicionado nióbio, a respeito de sua temperabilidade. Dilatometricamente traçou-se a curva TTT desse material, bem como a de um ferro fundido branco de alto cromo para efeito comparativo. Constatou-se por essa comparação e pelos resultados da literatura a alta temperabilidade obtida pela liga experimental. A partir da temperatura de austenitização utilizada, podem-se usar taxas de resfriamento de até 0,12°C/s sem transformação de fase, enquanto que na liga comparativa essa taxa aumenta para 5,8°C/s. Foram realizadas análises de desgaste abrasivo, de dureza e microdureza, de difração por raios-X , de fase magnética e de microanálise como forma de caracterizar as transformações de fase observadas por dilatometria. As variações estruturais decorrentes dos tratamentos térmicos realizados nas duas ligas foram acompanhados por microscopia ótica. É indicativo pelo presente trabalho que tal material além de suas características inerentes de resistência à abrasão e à corrosão oferece maior flexibilidade nos projetos que envolvam paredes espessas. / In this work we studied the hardenability of high chromium- molibdenum white cast iron with niobium. By dilatometry we obtained the TTT curve of this material as well as the high chromium white cast iron for comparison. This comparison and available results in literature confirm the high temperability of experimental material. We can use slow rate cooling 0,12°C/s or higher without phase transformation, while in the comparative alloy this rate is around 5,8°C/s or higher from specific used austenitic abrasive temperature. We also realized analysis of abrasive wear, hardness and microhardness, raios-X difraction, magnetic phase and microanalyse for verifing the phase transformation as observed by dilatometry. The structure variation as function of termic treatment in both alloys is monitored by optical microscope. The present work indicate that the material under study can offer more flexibility for projects with thick materials apart from intrinsic characteristics of abrasive wear and corrosion.