Multiscale morphology design of hybrid halide perovskites through a polymeric template

Hybrid halide perovskites have emerged as promising active constituents of next generation solution processable optoelectronic devices. During their assembling process, perovskite components undergo very complex dynamic equilibria starting in solution and progressing throughout film formation. Finding a methodology to control and affect these equilibria, responsible for the unique morphological diversity observed in perovskite films, constitutes a fundamental step towards a reproducible material processability. Here we propose the exploitation of polymer matrices as cooperative assembling components of novel perovskite CH3NH3PbI3 : polymer composites, in which the control of the chemical interactions in solution allows a predictable tuning of the final film morphology. We reveal that the nature of the interactions between perovskite precursors and polymer functional groups, probed by Nuclear Magnetic Resonance (NMR) spectroscopy and Dynamic Light Scattering (DLS) techniques, allows the control of aggregates in solution whose characteristics are strictly maintained in the solid film, and permits the formation of nanostructures that are inaccessible to conventional perovskite depositions. These results demonstrate how the fundamental chemistry of perovskite precursors in solution has a paramount influence on controlling and monitoring the final morphology of CH3NH3PbI3 (MAPbI3) thin films, foreseeing the possibility of designing perovskite : polymer composites targeting diverse optoelectronic applications.

Hybrid mathematical and informational modeling of beam-to-column connections

The analysis of steel and composite frames has traditionally been carried out by idealizing beam-to-column connections as either rigid or pinned. Although some advanced analysis methods have been proposed to account for semi-rigid connections, the performance of these methods strongly depends on the proper modeling of connection behavior. The primary challenge of modeling beam-to-column connections is their inelastic response and continuously varying stiffness, strength, and ductility. In this dissertation, two distinct approaches—mathematical models and informational models—are proposed to account for the complex hysteretic behavior of beam-to-column connections. The performance of the two approaches is examined and is then followed by a discussion of their merits and deficiencies. To capitalize on the merits of both mathematical and informational representations, a new approach, a hybrid modeling framework, is developed and demonstrated through modeling beam-to-column connections. Component-based modeling is a compromise spanning two extremes in the field of mathematical modeling: simplified global models and finite element models. In the component-based modeling of angle connections, the five critical components of excessive deformation are identified. Constitutive relationships of angles, column panel zones, and contact between angles and column flanges, are derived by using only material and geometric properties and theoretical mechanics considerations. Those of slip and bolt hole ovalization are simplified by empirically-suggested mathematical representation and expert opinions. A mathematical model is then assembled as a macro-element by combining rigid bars and springs that represent the constitutive relationship of components. Lastly, the moment-rotation curves of the mathematical models are compared with those of experimental tests. In the case of a top-and-seat angle connection with double web angles, a pinched hysteretic response is predicted quite well by complete mechanical models, which take advantage of only material and geometric properties. On the other hand, to exhibit the highly pinched behavior of a top-and-seat angle connection without web angles, a mathematical model requires components of slip and bolt hole ovalization, which are more amenable to informational modeling. An alternative method is informational modeling, which constitutes a fundamental shift from mathematical equations to data that contain the required information about underlying mechanics. The information is extracted from observed data and stored in neural networks. Two different training data sets, analytically-generated and experimental data, are tested to examine the performance of informational models. Both informational models show acceptable agreement with the moment-rotation curves of the experiments. Adding a degradation parameter improves the informational models when modeling highly pinched hysteretic behavior. However, informational models cannot represent the contribution of individual components and therefore do not provide an insight into the underlying mechanics of components. In this study, a new hybrid modeling framework is proposed. In the hybrid framework, a conventional mathematical model is complemented by the informational methods. The basic premise of the proposed hybrid methodology is that not all features of system response are amenable to mathematical modeling, hence considering informational alternatives. This may be because (i) the underlying theory is not available or not sufficiently developed, or (ii) the existing theory is too complex and therefore not suitable for modeling within building frame analysis. The role of informational methods is to model aspects that the mathematical model leaves out. Autoprogressive algorithm and self-learning simulation extract the missing aspects from a system response. In a hybrid framework, experimental data is an integral part of modeling, rather than being used strictly for validation processes. The potential of the hybrid methodology is illustrated through modeling complex hysteretic behavior of beam-to-column connections. Mechanics-based components of deformation such as angles, flange-plates, and column panel zone, are idealized to a mathematical model by using a complete mechanical approach. Although the mathematical model represents envelope curves in terms of initial stiffness and yielding strength, it is not capable of capturing the pinching effects. Pinching is caused mainly by separation between angles and column flanges as well as slip between angles/flange-plates and beam flanges. These components of deformation are suitable for informational modeling. Finally, the moment-rotation curves of the hybrid models are validated with those of the experimental tests. The comparison shows that the hybrid models are capable of representing the highly pinched hysteretic behavior of beam-to-column connections. In addition, the developed hybrid model is successfully used to predict the behavior of a newly-designed connection.

Hybrid materials for biomedical applications

The increased longevity of humans and the demand for a better quality of life have led to a continuous search for new implant materials. Scientific development coupled with a growing multidisciplinarity between materials science and life sciences has given rise to new approaches such as regenerative medicine and tissue engineering. The search for a material with mechanical properties close to those of human bone produced a new family of hybrid materials that take advantage of the synergy between inorganic silica (SiO4) domains, based on sol-gel bioactive glass compositions, and organic polydimethylsiloxane, PDMS ((CH3)2.SiO2)n, domains. Several studies have shown that hybrid materials based on the system PDMS-SiO2 constitute a promising group of biomaterials with several potential applications from bone tissue regeneration to brain tissue recovery, passing by bioactive coatings and drug delivery systems. The objective of the present work was to prepare hybrid materials for biomedical applications based on the PDMS-SiO2 system and to achieve a better understanding of the relationship among the sol-gel processing conditions, the chemical structures, the microstructure and the macroscopic properties. For that, different characterization techniques were used: Fourier transform infrared spectrometry, liquid and solid state nuclear magnetic resonance techniques, X-ray diffraction, small-angle X-ray scattering, smallangle neutron scattering, surface area analysis by Brunauer–Emmett–Teller method, scanning electron microscopy and transmission electron microscopy. Surface roughness and wettability were analyzed by 3D optical profilometry and by contact angle measurements respectively. Bioactivity was evaluated in vitro by immersion of the materials in Kokubos’s simulated body fluid and posterior surface analysis by different techniques as well as supernatant liquid analysis by inductively coupled plasma spectroscopy. Biocompatibility was assessed using MG63 osteoblastic cells. PDMS-SiO2-CaO materials were first prepared using nitrate as a calcium source. To avoid the presence of nitrate residues in the final product due to its potential toxicity, a heat-treatment step (above 400 °C) is required. In order to enhance the thermal stability of the materials subjected to high temperatures titanium was added to the hybrid system, and a material containing calcium, with no traces of nitrate and the preservation of a significant amount of methyl groups was successfully obtained. The difficulty in eliminating all nitrates from bulk PDMS-SiO2-CaO samples obtained by sol-gel synthesis and subsequent heat-treatment created a new goal which was the search for alternative sources of calcium. New calcium sources were evaluated in order to substitute the nitrate and calcium acetate was chosen due to its good solubility in water. Preparation solgel protocols were tested and homogeneous monolithic samples were obtained. Besides their ability to improve the bioactivity, titanium and zirconium influence the structural and microstructural features of the SiO2-TiO2 and SiO2-ZrO2 binary systems, and also of the PDMS-TiO2 and PDMS-ZrO2 systems. Detailed studies with different sol-gel conditions allowed the understanding of the roles of titanium and zirconium as additives in the PDMS-SiO2 system. It was concluded that titanium and zirconium influence the kinetics of the sol-gel process due to their different alkoxide reactivity leading to hybrid xerogels with dissimilar characteristics and morphologies. Titanium isopropoxide, less reactive than zirconium propoxide, was chosen as source of titanium, used as an additive to the system PDMS-SiO2-CaO. Two different sol-gel preparation routes were followed, using the same base composition and calcium acetate as calcium source. Different microstructures with high hydrophobicit were obtained and both proved to be biocompatible after tested with MG63 osteoblastic cells. Finally, the role of strontium (typically known in bioglasses to promote bone formation and reduce bone resorption) was studied in the PDMS-SiO2-CaOTiO2 hybrid system. A biocompatible material, tested with MG63 osteoblastic cells, was obtained with the ability to release strontium within the values reported as suitable for bone tissue regeneration.

Design of functional hybrid coatings with anti-biofouling, self-cleaning and anti-reflecting applications

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Development of hybrid composites for automotive applications: effect of addition of SEBS on the morphology, mechanical, viscoelastic, crystallization and thermal degradation properties of PP/PS-xGnP composites

In this article, we report on a simple and cost effective approach for the development of light-weight, super-tough and stiff material for automotive applications. Nanocomposites based on PP/PS blend and exfoliated graphene nanoplatelets (xGnP) were prepared with and without SEBS. Mechanical, crystallization and thermal degradation properties were determined and correlated with phase morphology. The addition of xGnP to PP/PS blend increased the tensile modulus at the expense of toughness. The presence of xGnP increased the enthalpy of crystallization and enthalpy of fusion of PP in the blends, without affecting segmental mobility and thermal stability. Addition of polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SEBS) improved the toughness of PP/PS blends, but decreased the stiffness. The incorporation of xGnP into this ternary blend generated a super-tough material with improved stiffness and tensile elongation, suitable for automotive applications. It is observed that the presence of SEBS diminished the tendency of agglomeration of xGnP and their unfavorable interactions with thermoplastics, which in turn reduced the internal friction in the matrix.

Multi-scale simulation using a hybrid mass-spring system and finite element model

Ply-scale finite element (FE) models are widely used to predict the performance of a composite structure based on material properties of individual plies. When simulating damage, these models neglect microscopic fracture processes which may have a significant effect on how a crack progresses within and between plies of a multidirectional laminate. To overcome this resolution limitation a multi-scale modelling technique is employed to simulate the effect micro-scale damage events have on the macro-scale response of a structure. The current paper discusses the development and validation of a hybrid mass-spring system and finite element modelling technique for multi-scale analysis. The model developed here is limited to elastic deformations; however, it is the first key step towards an efficient multi-scale damage model well suited to simulation of fracture in fibre reinforced composite materials. Various load cases have been simulated using the model developed here which show excellent accuracy compared to analytical and FE results. Future work is discussed, including extension of the model to incorporate damage modelling.

A hybrid embedded cohesive element method for predicting matrix cracking in composites

The complex architecture of many fibre-reinforced composites makes the generation of finite element meshes a labour-intensive process. The embedded element method, which allows the matrix and fibre reinforcement to be meshed separately, offers a computationally efficient approach to reduce the time and cost of meshing. In this paper we present a new approach of introducing cohesive elements into the matrix domain to enable the prediction of matrix cracking using the embedded element method. To validate this approach, experiments were carried out using a modified Double Cantilever Beam with ply drops, with the results being compared with model predictions. Crack deflection was observed at the ply drop region, due to the differences in stiffness, strength and toughness at the bi-material interface. The new modelling technique yields accurate predictions of the failure process in composites, including fracture loads and crack deflection path.

CFRP-Steel hybrid retrofitting of steel-concrete composite structures

Carbon fiber reinforced polymer (CFRP) is found to be an effective material for the retrofitting of both reinforced concrete (RC) and steel structures. However, retrofitting such structures using CFRP alone is shown to exhibit a premature failure due to early de-bonding of the CFRP laminates from the hosting sur-faces. On the other hand, steel plates are also used separately for the steel and RC structures. However, steel plates usually add the self-weight to the structures whereas CFRP is known for its high strength to weight ra-tio. In the present study, the advantages of both steel plates and CFRP is used to form a hybrid retrofitting sys-tem that is able to withstand the existing load to prevent the failure of the structures. In order to improve the retrofitting efficiency of a steel-concrete composite structures, an experimental investigation is carried out to examine the use of effectiveness of CFRP-steel hybrid retrofitting system.

The difference of Being in the early modern world: a relational-material approach to life in Scotland in the period of the witch trials

This thesis investigates how ways of being in different ontologies emerge from material and embodied practice. This general concern is explored through the particular case study of Scotland in the period of the witch trials (the 16th and 17th centuries C.E.). The field of early modern Scottish witchcraft studies has been active and dynamic over the past 15 years but its prioritisation of what people said over what they did leaves a clear gap for a situated and relational approach focusing upon materiality. Such an approach requires a move away from the Cartesian dichotomies of modern ontology to recognise past beliefs as real to those who experienced them, coconstitutive of embodiment and of the material worlds people inhabited. In theory, method and practice, this demands a different way of exploring past worlds to avoid flattening strange data. To this end, the study incorporates narratives and ‘disruptions’ – unique engagements with Contemporary Art which facilitate understanding by enabling the temporary suspension of disbelief. The methodology is iterative, tacking between material and written sources in order to better understand the heterogeneous assemblages of early modern (counter-) witchcraft. Previously separate areas of discourse are (re-)constituted into alternative ontic categories of newly-parallel materials. New interpretations of things, places, bodies and personhoods emerge, raising questions about early modern experiences of the world. Three thematic chapters explore different sets of collaborative agencies as they entwine into new things, co-fabricating a very different world. Moving between witch trial accounts, healing wells, infant burial grounds, animals, discipline artefacts and charms, the boundaries of all prove highly permeable. People, cloth and place bleed into one another through contact; trees and water emerge as powerful agents of magical-place-making; and people and animals meet to become single, hybrid-persons spread over two bodies. Life and death consistently emerge as protracted processes with the capacity to overlap and occur simultaneously in problematic ways. The research presented in this thesis establishes a new way of looking at the nature of Being as experienced by early modern Scots. This provides a foundation for further studies, which can draw in other materials not explored here such as communion wares and metal charms. Comparison with other early modern Western societies may also prove fruitful. Furthermore, the methodology may be suitable for application to other interdisciplinary projects incorporating historical and material evidence.

Determination of preventive maintenance lead time using hybrid analysis

The time for conducting Preventive Maintenance (PM) on an asset is often determined using a predefined alarm limit based on trends of a hazard function. In this paper, the authors propose using both hazard and reliability functions to improve the accuracy of the prediction particularly when the failure characteristic of the asset whole life is modelled using different failure distributions for the different stages of the life of the asset. The proposed method is validated using simulations and case studies.