19 Dec 2004. / Published through the Information Bridge: DOE Scientific and Technical Information. "IS-T 1983" Fei Tang. 12/19/2004. Report is also available in paper and microfiche from NTIS.

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Os aços inoxidáveis endurecidos por precipitação vêm sendo largamente empregados na indústria aeronáutica, por combinar resistência mecânica, tenacidade à fratura e resistência à corrosão. E deste modo, são materiais que possibilitam a substituição dos aços carbonos utilizados atualmente, que necessitam de tratamento superficial adicional, como o cádmio, para melhorar a resistência à corrosão. A utilização desses revestimentos traz desvantagens como o custo, a fabricação, a susceptibilidade à fragilização por hidrogênio além dos aspectos ambientais. Neste contexto, o aço endurecido por precipitação UNS S46500, designado como Custom 465® foi avaliado considerando o efeito da temperatura de envelhecimento sobre as propriedades mecânicas e a resistência à corrosão por pite. Amostras tratadas nas condições solubilizada e envelhecida a 510ºC (H950) e 538ºC (H1000) foram submetidas ao ensaio de tração, caracterização microestrutural e ensaios de polarização potenciodinâmica (PP) para determinar a resistência à corrosão por pite. Os exames microestruturais foram realizados com auxílio de microscopia óptica (MO), microscopia eletrônica de varredura (MEV), espectroscopia de energia dispersiva (EDS) e difração de raios X. Também foram realizadas análises utilizando o software Thermo-Calc. A resistência à corrosão por pite foi avaliada em solução 0,6M NaCl com adições crescentes de Na2SO4. Os resultados obtidos nos ensaios de PP nas duas condições de tratamento térmico foram comparados entre si e com resultados disponíveis na literatura (CALDERÓN-HERNANDEZ, 2012) para o aço inoxidável UNS S30403 (304L). Os exames e análises da microestrutura revelaram que o aço Custom 465® envelhecido apresenta uma matriz martensítica, precipitados de fase chi, austenita e precipitados Ni3Ti. O tratamento H950 apresentou maior resistência mecânica e menor alongamento do que o tratamento H1000. Tal comportamento foi devido à produção de maior porcentagem de fase chi e menor porcentagem de austenita nesse tratamento de envelhecimento. Os diferentes tratamentos térmicos, condição solubilizada, H950 e H1000 apresentaram praticamente a mesma resistência à corrosão por pite. Por outro lado, o aço Custom 465® apresentou ótima resposta à inibição da nucleação de pite com adições crescentes de sulfato em meio de 0,6M NaCl, sendo que a condição H1000 se sobressai sobre a H950 nessa questão. Além disso, através da adição de sulfato foi 7 possível obter maior resistência a corrosão por pite do aço Custom 465® comparativamente ao aço 304L. Tal comportamento foi discutido em termos da afinidade química entre níquel, cloreto e sulfato, levando a maior resistência à corrosão por pite quando o aço contém maior teor de níquel (que é o caso do aço Custom 465®). Este trabalho indicou que o critério na escolha do tratamento de envelhecimento do aço Custom 465® deve ser o das propriedades mecânicas almejadas, uma vez que a resistência à corrosão por pite mostrou-se praticamente independente do tratamento térmico. / The precipitation hardened stainless steels have been widely used in the aircraft industry to combine mechanical strength, fracture toughness and corrosion resistance. And therefore, are materials that enable replacement of the carbon steels used today, which require additional surface treatment, such as cadmium plating, to improve the corrosion resistance. The use of such coatings brings disadvantages such as cost, manufacturing, susceptibility to hydrogen embrittlement beyond environmental aspects. In this context, the precipitation hardened steel UNS S46500, known as Custom 465® were evaluated for the effect of aging temperature on the mechanical properties and the resistance to pitting corrosion .Treated samples in solubilized and aged condition at 510°C (H950) and 538ºC (H1000) were subjected to tensile strength test, microstructural characterization and potentiodynamic polarization (PP) tests to determine the pitting corrosion resistance. The microstructural studies were performed with the aid of optical microscopy (OM), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction. Analyzes were also performed using the Thermo -Calc software. The resistance to pitting corrosion was evaluated at 0.6M NaCl solution with increasing additions of Na2SO4. The results obtained from tests of PP in both heat treatment conditions were compared with each other and with results available in the literature (CALDERÓN HERNANDEZ, 2012) to stainless steel UNS S30403 (304L). The analysis of the microstructure revealed that the steel aged Custom 465 ® presents a martensitic matrix, chi precipitates, Ni3Ti precipitates and austenite phase. The H950 age treatment had higher mechanical strength and lower elongation than the treatment H1000. Such behavior was due to the production of higher percentage of chi and a lower percentage of austenite phase in aging treatment. The different heat treatments, solubilized condition, H950 and H1000 showed almost the same pitting corrosion resistance. On the other hand, the Custom 465® showed good response to pitting inhibition with increasing nucleating additions of sulfate in 0.6M NaCl, with enhanced result for H1000 condition. Furthermore, by adding sulfate was possible to obtain greater pitting corrosion resistance of Custom 465® compared to the 304L steel. This behavior has been discussed in terms of the chemical affinity between nickel, chloride and sulphate, leading to higher pitting corrosion resistance when the steel contains a higher nickel 9 content (which is the case of steel Custom 465®). This study indicates that the criterion in selecting the aging heat treatment of Custom 465® steel must be the desired mechanical properties, since the pitting corrosion resistance was found to be substantially independent of heat treatment.

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Les exigences des clients du secteur aéronautique imposent aux entreprises de prendre en compte pour le dimensionnement les effets de la température sur toute la durée de vie du produit. Cependant, aucune loi ne permet actuellement de prévoir l’impact du vieillissement thermique sur le comportement des matériaux. Ce travail a pour objectif de comprendre le mécanisme de vieillissement thermique des alliages d’aluminium et son impact sur les propriétés mécaniques, mais surtout d’acquérir un outil performant capable d’obtenir rapidement des données matériaux après vieillissement.Au cours de cette étude, de nombreuses analyses microstructurales et mécaniques ont été réalisées sur trois alliages d’aluminium à durcissement structural. Différentes combinaisons temps-température de vieillissement ont été testées afin de disposer d’une large base de données sur ces matériaux (caractéristiques mécaniques statiques Rm, Rp0,2 et dureté et tailles des précipités durcissants). Ces données ont ensuite été compilées dans un modèle de vieillissement basé sur les théories classiques de durcissement structural, de croissance et de coalescence des précipités.Le modèle de vieillissement créé répond au besoin initial et prédit de façon conservative le comportement mécanique des alliages ayant subi un vieillissement thermique isotherme. Des axes d’amélioration sont envisagés pour ce modèle évolutif, comme l’intégration de la prévision du comportement en fatigue ainsi que le traitement de cas anisothermes pour une représentation plus réelle des conditions de service des pièces aéronautiques. / In aeronautics, customers ask companies to consider the effects of temperature over the entire life of the product in structural requirements. Indeed, aircraft parts are demanded to last longer (up to 90 000 hours) and operate at higher temperatures (up to 250°C). No laws enable to predict the impact of thermal ageing on materials behavior. Current practices are to perform mechanical testing after ageing in ovens at various temperatures, but they are expensive and incompatible with the development schedules. This work aims to understand the thermal aging mechanism of aluminum alloys and its impact on mechanical properties, but especially to acquire a powerful tool able to quickly obtain material data after aging.During this study, many microstructural and mechanical analyses were conducted on three precipitation hardened aluminum alloys. Different combinations of aging time and temperature were tested to get a large database of these materials (static mechanical characteristics Rm, Rp0,2 and hardness and sizes of hardening precipitates). These data were then compiled into a computing aging model based on the classical theories of precipitation hardening, growth and coarsening of precipitates.The created aging model responds to the initial need and can conservatively predict the mechanical behavior of aluminum alloys under isothermal aging. Improvement areas are considered for this evolutionary model, such as the integration of fatigue behavior prediction and the inclusion of thermal cycles for a more realistic representation of service conditions of aircraft parts.

In the presented dissertation thesis, I closely focused on corrosion resistance of non-ferrous metals. For full understanding of the possibilities for increasing corrosion resistance, it was vital to initially recognize the influences to the corrosion system of the samples and their surrounding environment. For this purpose, I focused on heat treatment, corrosion, and protective coatings, in the theoretical part of the thesis. For the subsequent research, it was necessary to define several constant variables, first. For this purpose, I have chosen a group of magnesium alloys, namely AZ91 Alloy and 3.5 % NaCl Electrolyte. AZ91 Alloy is of heterogenous structure formed by a solid solution of aluminum in magnesium, intermetallic phase in Mg17Al12, and their eutectic. Local microcells tend to occur in these heterogenities, which leads to faster corrosion. In order to increase corrosion resistance of the alloy, I used a combination of heat treatment and protective phosphate coating. For creating of the desired structure, which further affects compact coating formation, I selected a process involving solution heating with precipitation hardening T6. Secondary goals of the thesis involved optimization of standard technical procedures for the sake of increasing efficiency. With regard to this goal, I introduced optimized heat treatment T6 using accelerated cooling of a sample in water and liquid nitrogen. A modification besides the standard phosphating procedure was carried out with no activation step. For evaluation of corrosion resistance of the samples, I conducted water immersion tests using electrochemical methods; such as potenciodynamic curves combined with electrochemical impedance spectroscopy. In order to streamline the evaluation of the corrosion surface in technical practice, I used automatic detection. Substantial improvement of corrosion resistance of the above mentioned system, compared to heat-untreated samples, was proven through electrochemical methods. Due to accelerated cooling, a more homogeneous structure was achieved, which could be further utilized to create more uniform protective coating. For some phosphate coating, specifically manganese phosphate coating, I identified certain modifications that were in line with the set goals; i.e. skipping the activation phase, and using automatic detection for evaluation of uniform corrosion on the samples.

The methods of MSD are applied to the design of functionally graded materials. Analysis models are presented to allow the design of compliant derailleur for a case study and constraints are placed on the design. Several methods are presented for relating elements of the microstructure to the properties of the material, including Taylor yield theory, Hill elastic bounds, and precipitation hardening. Applying n-point statistics to the MSD framework is also discussed. Some results are presented for the information content of the 2-point correlation statistics that follow from the methods used to integrate functionally graded materials into MSD. For the compliant beam case study, the best design (98%Al-2%Li) was a 97% improvement over the worst (100%Al). The improvements were primarily due to the precipitation hardening, although anisotropy also significantly impacted the design. Under the constraints for the design, allowing the beam to be functionally graded had little effect on the overall design, unless there was significant stiffening occurring along with particulate formation.

Commercial alloys are continuously developed to improve their performance. Therefore it is important to develop new optimisation software, which could be used in development of new materials or in materials selection. In this study the mechanical properties which are important in materials selection in mechanical design are investigated. Two types of materials are analysed, aluminium alloys and stainless steels but focus will be on the aluminium alloys. Thermodynamic analysis has been used to evaluate the effect of the microstructure. Solid solution hardening has been successfully modelled for both aluminium alloys and stainless steels and follows the theories by Labusch and Nabarro. The precipitation hardening is most dominant for the hardenable aluminium alloys, but the non-hardenable alloys also increase their strength from precipitation hardening. The non-hardenable alloys are divided into tempers, which differ in the amount of strain hardening. This has also been modelled successfully. Combining these fundamental results with multiple regression, models for mechanical properties have been created. Separate models are developed for wrought aluminium alloys and stainless steels. For the aluminium alloys this includes the solid solution hardening and the precipitation hardening. For the stainless steels the thickness, nitrogen content and ferrite content are included together with the solid solution hardening. / QC 20101122

This research focused on a comprehensive microstructural and mechanical property characterisation study of the Ni-Fe-Cr alloys 718 and 945X. The aim of the project was to better understand the relationship between performance and microstructure of existing (Alloy 718) and newly developed (Alloy 945X) high strength nickel alloys focusing on downhole applications. The main difference between the two alloys is that alloy 945X has lower Nb content than alloy 718, which may minimise the tendency to form delta when combined with correct processing. Previous studies have related the hydrogen embrittlement in alloy 718 with the collection of hydrogen by delta phase. Microstructural characterisation of the new alloy 945X after long term isothermal exposure up to 120 hours in the temperature range 650◦C to 900◦C was conducted with scanning electron microscopy (SEM), to generate a time-temperature-transformation (TTT) diagram. The TTT diagram was used as a road map for designing two isothermal heat treatments of alloy 945X on tensile specimens. Then, the effect of hydrogen charging on the tensile properties and microstructure of the 'as-received' and these two variant heat treatments was investigated. Fractographic analysis showed that, in the presence of hydrogen, intergranular fracture occurred for all the heat treatments, regardless the presence of delta phase at grain boundaries. There was no simple correlation between the volume fraction of delta-phase and susceptibility to hydrogen assisted embrittlement. Rather, it was demonstrated that the morphology and distribution of delta-phase along grain boundaries plays a key role and the other precipitate phases also have an influence through their effect on the ease of strain localisation. This study also examined the hydrogen embrittlement sensitivity of nickel alloy 718 given four different heat treatments to obtain various microstructural states. Each heat treatment leads to differences in the precipitate morphologies of γ', γ'' and delta phases. Material characterisation and fractography of the examined heat treatments were performed using a high resolution FEG-SEM. Three specimens of each condition were pre- charged with hydrogen and tensile properties were compared with those of non-charged specimens. It was observed that hydrogen embrittlement was associated with intergranular and transgranular microcrack formation, leading to an intergranular brittle fracture. delta phase may assist the intergranular crack propagation, and this was shown to be particularly true when this phase is coarse enough to produce crack initia- tion, but this is not the only factor determining embrittlement. Other microstructural features play a role, as does the strength of the material. Finally, the evolution of delta-(Ni3Nb) phase in alloy 718 from the early stages of precipitation, with a particular focus on identifying the grain boundary characteristics that favour precipitation of grain boundary delta phase was investigated. Results showed that delta phase was firstly formed on Σ3 boundaries after 5 hours at the examined temperature (800◦C). Increasing ageing time at 800◦C was observed to lead to an increase in size and precipitation of phases γ'-γ''-delta, an increase in fraction of the special CSL boundaries and an evolution in the morphology of twins and the growth of grains.

The need for clean and renewable fuel such as hydrogen is driven by a growing worldwide population and increasing air pollution from fossil fuels. One of the major barriers for the use of hydrogen in automotive industry is the storage of hydrogen. Physisorption is the most promising storage technique due to its high storage density, reversibility and rapid sorption kinetics besides being safe and volume-efficient. A major challenge for physisorption is the need to manage the heat of adsorption at cryogenic temperatures. In this thesis, a 6061 aluminum microchannel cooling plate is designed to remove the equivalent heat flux required by the adsorption of hydrogen within an adsorption bed. Therefore, the objective of this thesis is to determine whether laser welding and heat treating strategies can be developed for a 6061 aluminum microchannel cooling plate as part of a larger hydrogen storage thermal management system. Key manufacturing process requirements include controlling the hermeticity, strength and dimensional stability of the heat-treated weld joint. A hermetic microchannel cooling plate was successfully laser welded and heat treated using free convection in air to quench the solution heat treatment. The weld strength and warpage obtained were within acceptable limits. Experimental testing of the fabricated microchannel cooling plate showed acceptable percent error with an experimental heat removal rate within 13.4% of computational fluid dynamics (CFD) analyses and an average pressure drop error of 25%. Calculations show that the cooling plate developed could support a hydrogen storage thermal management system taking up 5.0% and 10.3% of the system displacement volume and mass, respectively. / Graduation date: 2013