A New Phenomenon: Sub-Tg, Solid-State, Plasticity-Induced Bonding in Polymers

Polymer self-adhesion due to the interdiffusion of macromolecules has been an active area of research for several decades [70, 43, 62, 42, 72, 73, 41]. Here, we report a new phenomenon of sub-Tg, solid-state, plasticity-induced bonding; where amorphous polymeric films were bonded together in a period of time on the order of a second in the solid-state at ambient temperatures nearly 60 K below their glass transition temperature (Tg) by subjecting them to active plastic deformation. Despite the glassy regime, the bulk plastic deformation triggered the requisite molecular mobility of the polymer chains, causing interpenetration across the interfaces held in contact. Quantitative levels of adhesion and the morphologies of the fractured interfaces validated the sub-Tg, plasticity-induced, molecular mobilization causing bonding. No-bonding outcomes (i) during the compression of films in a near hydrostatic setting (which inhibited plastic flow) and (ii) between an 'elastic' and a 'plastic' film further established the explicit role of plastic deformation in this newly reported sub-Tg solid-state bonding

Dynamic scaling in vacancy-mediated disordering

We consider the disordering dynamics of an interacting binary alloy with a small admixture of vacancies which mediate atom-atom exchanges. Starting from a perfectly phase-segregated state, the system is rapidly heated to a temperature in the disordered phase. A suitable disorder parameter, namely, the number of broken bonds, is monitored as a function of time. Using Monte Carlo simulations and a coarse-grained field theory, we show that the late stages of this process exhibit dynamic scaling, characterized by a set of scaling functions and exponents. We discuss the universality of these exponents and comment on some subtleties in the early stages of the disordering process.Comment: 15 pages, 6 figure

Mechanisms of High Temperature Degradation of Thermal Barrier Coatings.

Thermal barrier coatings (TBCs) are crucial for increasing the turbine inlet temperature (and hence efficiency) of gas turbine engines. The thesis describes PhD research aimed at improving understanding of the thermal cycling failure mechanisms of electron beam physical vapour deposited (EB-PVD) yttria stabilised zirconia (YSZ) TBCs on single crystal superalloys. The research consisted of three different stages. The first stage involved designing a coupled one-dimensional thermodynamic-kinetic oxidation and diffusion model capable of predicting the concentration profiles of alloying elements in a single-phase γ nickel-rich Ni-Al-Cr ternary alloy by the finite difference method. The aim of this investigation was to improve the understanding of interactions between alloying species and developing oxide. The model demonstrated that in the early stages of oxidation, Al consumption by oxide scale growth is faster than Al replenishment by diffusion towards the scale, resulting in an initial Al depletion in the alloy near the scale. The second stage involved a systematic study of the life-time of TBC systems on different single crystal superalloys. The study aimed at demonstrating that the compatibility of modern nickel-based single crystal superalloys with TBC systems is influenced strongly by the content of alloying element additions in the superalloy substrate. The results can be explained by postulating that the fracture toughness parameters controlling decohesion are influenced strongly by small changes in composition arising from interdiffusion with the bond coat, which itself inherits elemental changes from the substrate. The final stage of study involved a detailed study of different bond coats (two β-structured Pt-Al types and a γ/γ’ Pt-diffusion type) in TBC systems based on an EB-PVD YSZ top coat and a substrate material of CMSX-4 superalloy. Generation of stress in the thermally grown oxide (TGO) on thermal cycling, and its relief by plastic deformation and fracture, were investigated experimentally in detail

Primary crustal melt compositions: Insights into the controls, mechanisms and timing of generation from kinetics experiments and melt inclusions

We explore the controls, mechanisms and timing of generation of primary melts and their compositions, and show that the novel studies of melt inclusions in migmatites can provide important insights into the processes of crustal anatexis of a particular rock. Partial melting in the source region of granites is dependent on five main processes: (i) supply of heat; (ii) mineral–melt interface reactions associated with the detachment and supply of mineral components to the melt, (iii) diffusion in the melt, (iv) diffusion in minerals, and (v) recrystallization of minerals. As the kinetics of these several processes vary over several orders of magnitude, it is essential to evaluate in Nature which of these processes control the rate of melting, the composition of melts, and the extent to which residue–melt chemical equilibrium is attained under different circumstances. To shed light on these issues, we combine data from experimental and melt inclusion studies. First, data from an extensive experimental program on the kinetics of melting of crustal protoliths and diffusion in granite melt are used to set up the necessary framework that describes how primary melt compositions are established during crustal anatexis. Then, we use this reference frame and compare compositional trends from experiments with the composition of melt inclusions analyzed in particular migmatites. We show that, for the case of El Hoyazo anatectic enclaves in lavas, the composition of glassy melt inclusions provides important information on the nature and mechanisms of anatexis during the prograde suprasolidus history of these rocks, including melting temperatures and reactions, and extent of melt interconnection, melt homogenization and melt–residue equilibrium. Compositional trends in several of the rehomogenized melt inclusions in garnet from migmatites/granulites in anatectic terranes are consistent with diffusion in melt-controlled melting, though trace element compositions of melt inclusions and coexisting minerals are necessary to provide further clues on the nature of anatexis in these particular rocks.This work was supported by the National Science Foundation [grants EAR-9603199, EAR-9618867, EAR-9625517 and EAR-9404658], the Italian Consiglio Nazionale delle Ricerche, the European Commission (grant 01-LECEMA22F through contract No. ERAS-CT-2003-980409; and a H2020 Marie Skłodowska-Curie Actions under grant agreement No. 654606), the Italian Ministry of Education, University and Research (grants PRIN 2007278A22, 2010TT22SC and SIR RBSI14Y7PF), the Università degli Studi di Padova [Progetto di Ateneo CPDA107188/10 and a Piscopia—Marie Curie Fellowship under grant agreement No. 600376], the Australian Research Council (Australian Professorial Fellowship and Discovery Grants Nos. DP0342473 and DP0556700), and the National Research Foundation (South Africa; Incentives For Rated Researchers Program)

Routine characterization and interpretation of complex alkali feldspar intergrowths

Almost all alkali feldspar crystals contain a rich inventory of exsolution, twin, and domain microtextures that form subsequent to crystal growth and provide a record of the thermal history of the crystal and often of its involvement in replacement reactions, sometimes multiple. Microtextures strongly influence the subsequent behavior of feldspars at low temperatures during diagenesis and weathering. They are central to the retention or exchange of trace elements and of radiogenic and stable isotopes. This review is aimed at petrologists and geochemists who wish to use alkali feldspar microtextures to solve geological problems or who need to understand how microtextures influence a particular process. We suggest a systematic approach that employs methods available in most well founded laboratories. The crystallographic relationships of complex feldspar intergrowths were established by the 1970s, mainly using single-crystal X-ray diffraction, but such methods give limited information on the spatial relationships of the different elements of the microtexture, or of the mode and chronology of their formation, which require the use of microscopy. We suggest a combination of techniques with a range of spatial resolution and strongly recommend the use of orientated sections. Sections cut parallel to the perfect (001) and (010) cleavages are the easiest to locate and most informative. Techniques described are light microscopy; scanning electron microscopy using both backscattered and secondary electrons, including the use of surfaces etched in the laboratory; electron-probe microanalysis and analysis by energy-dispersive spectrometry in a scanning electron microscope; transmission electron microscopy. We discuss the use of cathodoluminescence as an auxiliary technique, but do not recommend electron-backscattered diffraction for feldspar work. We review recent publications that provide examples of the need for great care and attention to pre-existing work in microtextural studies, and suggest several topics for future work