Photo-oxidation in an O2 atmosphere: A powerful tool to elucidate the mechanism of UV-visible light oxidation of polymers - Application to the photodegradation of MDMO-PPV

This article describes a new approach to improve the analysis of the chemical modifications that result from the degradation of polymers under UV-visible light exposure in the presence of oxygen. The tool which is used consists of an irradiation chamber whose atmosphere is composed of ¹⁸O₂. The ¹⁸O₂ pressure inside the chamber and the hygrometry can be adjusted. In this study, particular attention was paid to the photo-oxidation of poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV). Using infrared spectroscopy, irradiation under the oxygen 18 atmosphere allowed discrimination between compounds formed via fixation of oxygen from the atmosphere and those formed by reorganisation of the matrix. In addition, irradiation of MDMO-PPV in an ¹⁸O₂ wet atmosphere allowed for detection of the presence of phenyl formate and aromatic ketone functions. This permitted validating the mechanism of photo-oxidation previously proposed. Additionally, with regard to blends made with MDMO-PPV and methano-fullerene[6,6]-phenyl C₆₁-butyric acid methyl ester ([60] PCBM), it was demonstrated that this technique facilitates the identification of the photo-oxidation products formed.     

Span-Restorable Mesh Networks with Multiple Quality of Protection (QoP) Service Classes

In the modern business environment there is considerable interest in being able to support a range of different transport service classes in an optical network, and charge accordingly. In this work we consider the capacity design problem for a mesh-restorable optical network supporting any mixture of four basic quality of protection (QoP) classes. The service definitions are (gold): assured restorability, (silver): best efforts, (bronze): non-protected and (economy): preemptible service. We give design models for optimal capacity design of span-restorable (or corresponding link-protected) mesh networks having any particular mixture of these service classes. We also apply and test the design models under several multi-QoP test case scenarios to gain insights about various strategies and options possible in a multi-QoP design environment. An interesting finding is that in some test cases, 15 to 30% of all demand can be in the gold class enjoying 100% restorability solely through preemption of economy class service capacity. This suggests the potential to design and operate mesh-based networks that have no spare capacity at all in the conventional sense: all capacity is bearing service of some paying type. The resulting frequency of preemption in the economy class services is also studied. Results also show typically high levels of best-efforts restorability in the silver class occurring in networks that are strictly designed only for the restorability of the gold class services. High restorability of best effort services, however, requires the preemption of economy services. These methods and findings can be used by network and business planners to evaluate a number of different service structuring, pricing, and capacity-design strategies that may offer advantages to them and new options for their customers.     

Development of a universal modeling tool for rechargeable lithium batteries

An interesting universal modeling tool for rechargeable lithium batteries is presented in this paper. The generic model is based on an equivalent circuit technique commonly used in electrochemical impedance characterization. Therefore, the parameters used in the model can be easily parameterized from the electrochemical impedance derivations, which provide a convenient integration with experimental cell characterizations. Such integration offers the universality in this modeling approach.     

Degradation of semiconducting polymers by concentrated sunlight

A lens based sunlight concentration setup was used to accelerate the degradation of semiconducting polymers. Sunlight was collected outdoor and focused into an optical fiber bundle allowing for indoor experimental work. Photo-degradation of several polymers was studied by UV-vis absorbance spectroscopy and infra-red spectroscopy. This showed that the degradation rate is significantly increased by increasing illumination intensity. Acceleration factors exceeding 100 compared to standard 1 sun illumination were observed for solar concentration of 200 suns in the case of P3HT. A comparison between infra-red spectra of MEH-PPV degraded at 1 sun intensity and at high solar concentration only showed minor deviations in degradation mechanisms. The acceleration factor was found to vary linearly with the solar concentration. Finally, a comparison of the degradation rates at 1 sun and 100 suns was carried out in a materials study employing five different conjugated polymers relevant to polymer solar cells for which acceleration factors in the range 19-55 were obtained.     

Improving the performances of earth air heat exchangers through Constructal design

Earth to air heat exchanger (EAHE) is a well‐known technique used to preheat or precool outdoor air before blowing it into a building. However, its geometry is often very simple as it consists in one or multiple straight pipes, while more complex arrangements can be found in heat exchangers design. In this paper, we explore the advantage of designing an EAHE as a network through the Constructal law point of view. A methodology is first proposed to design a single pipe EAHE when the need is defined in terms of cooling power, overall efficiency and enthalpy difference between the inlet air and the ground. Next, the single pipe EAHE is used as a reference for designing a tree‐shaped network under the constraint of identical fluid volume and cooling power. The geometrical features are allowed to change for the different branches of the network. The network coefficient of performance is found to increase significantly with the bifurcation level, illustrating the superior performances of the network. This approach was found to be robust as the improvements were not depending on the cooling demand or the environmental conditions. However, further work is needed to move from this theoretical result to practical considerations.     

Evaluation of commercial lithium-ion cells based on composite positive electrode for plug-in hybrid electric vehicle applications. Part I: Initial characterizations

Evaluating commercial Li-ion batteries presents some unique benefits. One of them is to use cells made from established fabrication process and form factor, such as those offered by the 18650 cylindrical configuration, to provide a common platform to investigate and understand performance deficiency and aging mechanism of target chemistry. Such an approach shall afford us to derive relevant information without influence from processing or form factor variability that may skew our understanding on cell-level issues. A series of 1.9 Ah 18650 lithium ion cells developed by a commercial source using a composite positive electrode comprising {LiMn_1/3Ni_1/3Co_1/3O₂ + LiMn₂O₄} is being used as a platform for the investigation of certain key issues, particularly path-dependent aging and degradation in future plug-in hybrid electric vehicle (PHEV) applications, under the US Department of Energy's Applied Battery Research (ABR) program. Here we report in Part I the initial characterizations of the cell performance and Part II some aspects of cell degradation in 2C cycle aging. The initial characterizations, including cell-to-cell variability, are essential for life cycle performance characterization in the second part of the report when cell-aging phenomena are discussed. Due to the composite nature of the positive electrode, the features (or signature) derived from the incremental capacity (IC) of the cell appear rather complex. In this work, the method to index the observed IC peaks is discussed. Being able to index the IC signature in details is critical for analyzing and identifying degradation mechanism later in the cycle aging study.     

Biodegradable Frequency‐Selective Magnesium Radio‐Frequency Microresonators for Transient Biomedical Implants

Bioresorbable implantable medical devices show a great potential for applications requiring medical care over well‐defined periods of time. Once their function is fulfilled, such implants naturally degrade and resorb in the body, which eliminates adverse long‐term effects or the need for a secondary surgery to extract the implanted device. Since biodegradable materials are water‐soluble, the fabrication of such transient electronic circuits and devices requires special care and needs to rely solely on dry processing steps without exposure to aqueous solutions. A further challenge is the in vivo powering of medical implants that are only constituted of biodegradable materials. This paper describes the design, fabrication, and testing of radio‐frequency biodegradable magnesium microresonators. To this end, an innovative microfabrication process with minimal exposure to aqueous media is developed to fabricate magnesium‐based, water‐soluble electronic components. It consists of a novel sequence of only three steps: one physical vapor deposition, one photolithography, and one ion beam etching step. The frequency‐selective wireless heating of different resonators is demonstrated. This represents a significant step toward their use as power receivers and microheaters in biodegradable implantable medical devices, for applications such as triggered drug release.     

Predictive Model of Graphene Based Polymer Nanocomposites: Electrical Performance

In this computational work, a new simulation tool on the graphene/polymer nanocomposites electrical response is developed based on the finite element method (FEM). This approach is built on the multi-scale multi-physics format, consisting of a unit cell and a representative volume element (RVE). The FE methodology is proven to be a reliable and flexible tool on the simulation of the electrical response without inducing the complexity of raw programming codes, while it is able to model any geometry, thus the response of any component. This characteristic is supported by its ability in preliminary stage to predict accurately the percolation threshold of experimental material structures and its sensitivity on the effect of different manufacturing methodologies. Especially, the percolation threshold of two material structures of the same constituents (PVDF/Graphene) prepared with different methods was predicted highlighting the effect of the material preparation on the filler distribution, percolation probability and percolation threshold. The assumption of the random filler distribution was proven to be efficient on modelling material structures obtained by solution methods, while the through-the –thickness normal particle distribution was more appropriate for nanocomposites constructed by film hot-pressing. Moreover, the parametrical analysis examine the effect of each parameter on the variables of the percolation law. These graphs could be used as a preliminary design tool for more effective material system manufacturing.     

Dynamics of Antimonene–Graphene Van Der Waals Growth

Van der Waals (vdW) heterostructures have recently been introduced as versatile building blocks for a variety of novel nanoscale and quantum technologies. Harnessing the unique properties of these heterostructures requires a deep understanding of the involved interfacial interactions and a meticulous control of the growth of 2D materials on weakly interacting surfaces. Although several epitaxial vdW heterostructures have been achieved experimentally, the mechanisms governing their synthesis are still nebulous. With this perspective, herein, the growth dynamics of antimonene on graphene are investigated in real time. In situ low‐energy electron microscopy reveals that nucleation predominantly occurs on 3D nuclei followed by a self‐limiting lateral growth with morphology sensitive to the deposition rate. Large 2D layers are observed at high deposition rates, whereas lower growth rates trigger an increased multilayer nucleation at the edges as they become aligned with the Z2 orientation leading to atoll‐like islands with thicker, well‐defined bands. This complexity of the vdW growth is elucidated based on the interplay between the growth rate, surface diffusion, and edges orientation. This understanding lays the groundwork for a better control of the growth of vdW heterostructures, which is critical to their large‐scale integration.