In commemoration of the Materials Research Society (MRS)’s 50th anniversary, the 2050 panel hosted a discussion to reflect on the past, present, and future of sustainability and the role of materials research and development. Three panelists discussed their views, based on their expertise, about future challenges and lessons from the past. Sustainable development is a broad topic; therefore, the discussion centered on their experience as material researchers and their efforts for a better and greener future. This work is developed in collaboration with the co-authors team, highlighting the need for accelerating research and development efforts, especially in materials science and applications, fostering interdisciplinary partnerships, and mobilizing collective action to address the complex and interconnected sustainability challenges that humanity is currently facing. This work highlights the perspectives of three material scientists and researchers on achieving a sustainable and healthy planet by 2050. It emphasizes the importance of decarbonization, electrification, and energy justice in reaching sustainable goals.
The United States has pledged to develop a 100% carbon-free electric power system by 2035 and a net-zero-emissions economy by 2050. While important advancements have been made in the scale, performance, and economics of clean energy technologies, meeting the nation's ambitious goals will not only require their deployment at scale, but also additional innovation and effective integration of different solutions. Technological developments across the broad suite of low-carbon energy solutions are advancing rapidly, with ongoing innovations in renewable electricity generation, industrial processes, and energy-saving technologies and services, including LED lighting, induction heating, electric vehicles, energy storage solutions, and mobility as a service, plus smart devices, controls, and more efficient and smart buildings. Combining renewable electricity with biotic and abiotic pathways to produce chemicals, fuels, and materials promises to deliver new solutions. Grid-interactive buildings and communities, integrating transportation infrastructure and vehicles, are likely to be significant components of any zero-carbon energy strategy. Low-carbon industrial manufacturing will also make strong contributions to a net-zero economy. While the technical prospects appear promising, variations in the state of infrastructure, jurisdictional and social equity, pollution, economic and socio-cultural constraints, energy resource availability, and supply chain dynamics found in different locations present a range of challenges and demand customized solutions. This paper provides a critical review and offers new insights into the technical, infrastructure, analytic, political, and economic challenges faced in translating the nation's ambitious net-zero-emissions goals into feasible and reliable implementation action plans.
Wind energy is anticipated to play a central role in enabling a rapid transition from fossil fuels to a system based largely on renewable power. For wind power to fulfill its expected role as the backbone – providing nearly half of the electrical energy – of a renewable-based, carbon-neutral energy system, critical challenges around design, manufacture, and deployment of land and offshore technologies must be addressed. During the past 3 years, the wind research community has invested significant effort toward understanding the nature and implications of these challenges and identifying associated gaps. The outcomes of these efforts are summarized in a series of 10 articles, some under review by Wind Energy Science (WES) and others planned for submission during the coming months. This letter explains the genesis, significance, and impacts of these efforts.
The transport of charge carriers throughout an active conjugated polymer (CP) host, characterized by a heterogeneous morphology of locally varying degrees of order and disorder, profoundly influences the performance of CP-based electronic devices, including diodes, photovoltaics, sensors, and supercapacitors. Out-of-plane charge carrier mobilities (μout-of-plane) across the bulk of the active material host and in-plane mobilities (μin-plane) parallel to a substrate are highly sensitive to local morphological features along their migration pathways. In general, the magnitudes of μout-of-plane and μin-plane are very different, in part because these carriers experience different morphological environments along their migration pathways. Suppressing the impact of variations in the morphological order/disorder on carrier migration remains an important challenge. While much is known about μin-plane and its optimization for devices, the current challenges are associated with μout-of-plane and its optimization for device performance. Therefore, this review is devoted to strategies for improving μout-of-plane in neat CP films and the implications for more complex systems, such as D:A blends which are relevant to OPV devices. The specific strategies discussed for improving μout-of-plane include solvent/field processing methods, chemical modification, thickness confinement, chemical additives, and different post-annealing strategies, including annealing with supercritical fluids. This review leverages the most recent fundamental understanding of mechanisms of charge transport and connections to morphology, identifying robust design strategies for targeted improvements of μout-of-plane.
The physical properties of polymer films of nanoscale thickness have been shown to exhibit film thickness-dependent behavior, largely associated with intermolecular interactions between the film and its external interfaces. These effects are typically manifested in the thickness dependencies of the glass transition temperatures (T(g)s), and segmental dynamics, over length scales ranging from a few nanometers to tens of nanometers in many polymer/substrate systems. Moreover, different experimental techniques, including incoherent neutron scattering, spectroscopic ellipsometry, and broadband dielectric spectroscopy, have yielded thickness-dependent T-g trends of the same systems that appear to be at odds. To this end, the first direct quantitative measurements of the length scales of interfacial interactions of strategically selected polymer/substrate systems, obtained using Kelvin force probe microscopy, are reported. These findings reveal pathways to understand and reconcile seemingly the contradictory experimental observations about T-g vs. film thickness trends, and dynamics, at the nanoscale. Our findings have broader implications for understanding the physical properties of polymer films in the nanoscale thickness regime.
Upon quenching a polymer melt to a temperature T below its glass transition temperature T-g, structural relaxations, physical aging, enable the material to return to equilibrium. Whereas the physical aging rate beta is independent of chain length for linear chain polymers, in the case of star-shaped polymers, beta depends on the functionality f (number of arms per molecule) and the degree of polymerization per arm N-arm; the dependence of beta on f, and on N-arm, is suppressed for large N-arm. Incoherent elastic neutron scattering measurements of star-shaped polystyrenes reveal that the mean square atomic vibrations decrease with increasing f. Consequently, the harmonic force constants kappa proportional to 1/, a measure of the local macromolecular stiffness, increase with decreasing f. This connection between the decrease of the aging rates and the increase of the molecular stiffness with increasing f is reported here for the first time, providing a rationale for understanding the aging of macromolecules of varying topologies.
Obesity-related type 2 diabetes (DM) is a major public health concern. Adipose tissue metabolic dysfunction, including fibrosis, plays a central role in DM pathogenesis. Obesity is associated with changes in adipose tissue extracellular matrix (ECM), but the impact of these changes on adipose tissue mechanics and their role in metabolic disease is poorly defined. This study utilized atomic force microscopy (AFM) to quantify difference in elasticity between human DM and non-diabetic (NDM) visceral adipose tissue. The mean elastic modulus of DM adipose tissue was twice that of NDM adipose tissue (11.50 kPa vs. 4.48 kPa) to a 95% confidence level, with significant variability in elasticity of DM compared to NDM adipose tissue. Histologic and chemical measures of fibrosis revealed increased hydroxyproline content in DM adipose tissue, but no difference in Sirius Red staining between DM and NDM tissues. These findings support the hypothesis that fibrosis, evidenced by increased elastic modulus, is enhanced in DM adipose tissue, and suggest that measures of tissue mechanics may better resolve disease-specific differences in adipose tissue fibrosis compared with histologic measures. These data demonstrate the power of AFM nanoindentation to probe tissue mechanics, and delineate the impact of metabolic disease on the mechanical properties of adipose tissue.
Harvested by advanced technical systems honed over decades of research and development, wind energy has become a mainstream energy resource. However, continued innovation is needed to realize the potential of wind to serve the global demand for clean energy. Here, we outline three interdependent, cross-disciplinary grand challenges underpinning this research endeavor. The first is the need for a deeper understanding of the physics of atmospheric flow in the critical zone of plant operation. The second involves science and engineering of the largest dynamic, rotating machines in the world. The third encompasses optimization and control of fleets of wind plants working synergistically within the electricity grid. Addressing these challenges could enable wind power to provide as much as half of our global electricity needs and perhaps beyond.
Work function modification of electrodes is an important factor to achieve high performance in organic electronics. However, a clear explanation of the origin of work function modification has remained elusive. Here, it is investigated how the work function of electrodes is affected by the charge-based through-space interaction with the well-known surface interaction. The studies reveal that the formation of a surface dipole leads to a work function shift, even when the work function modifying layer and substrate are separated. A work function shift is also demonstrated by electrophoretic deposition of ionic polyelectrolytes while the same polyelectrolytes do not cause any work function shift when they are spin cast. More noteworthy is that a neutral (nonionic) polymer which has no specific surface-interacting functional groups can induce work function shift of its substrate by a charge-based through-space interaction when deposited by electrospraying. These results provide a more comprehensive understanding of work function modification and motivate the design and selection of a wide range of effective work function modifying layers for organic electronics.
Spatial compositional heterogeneity strongly influences the dynamics of the A and B components of bulk miscible blends. Its effects are especially apparent in mixtures, such as poly(vinyl methyl ether) (PVME)/polystyrene (PS), where there exist significant disparities between the component glass transition temperatures (T(g)s) and relaxation times. The relaxation processes characterized by distinct temperature dependencies and relaxation rates manifest different local compositional environments for temperatures above and below the glass transition temperature of the miscible blend. This same behavior is shown to exist in miscible PS/PVME films as thin as 100 nm. Moreover, in thin films, the characteristic segmental relaxation times tau of the PVME component of miscible PVME/PS blends confined between aluminum (Al) substrates decrease with increasing molecular weight M of the PS component. These relaxation rates are film thickness dependent, in films up to a few hundred nanometers in thickness. This is in remarkable contrast to homopolymer films, where thickness confinement effects are apparent only on length scales on the order of nanometers. These surprisingly large length scales and M dependence are associated with the preferential interfacial enrichment-wetting layer formation-of the PVME component at the external Al interfaces, which alters the local spatial blend composition within the interior of the film. The implications are that the dynamics of miscible thin film blends are dictated in part by component T-g differences, disparities in component relaxation rates, component-substrate interactions, and chain lengths (entropy of mixing).
The role of self-assembled monolayers (SAMs), trichloro(1 H,1 H,2 H,2 H-perfluorooctyl) (FTS) and octadecyltrichlorosilane (OTS), deposited on indium tin oxide (ITO) substrates, on electronic properties of the poly(3-hexylthiophene) (P3HT)/SAM/ITO system is reported. SAMs, well known for modifying the surface energies of materials, are also known to modify the work functions (WFs) of semiconductors. Unsurprisingly, differences between the band-bending behaviors of P3HT/ITO, P3HT/OTS/ITO, and P3HT/FTS/ITO systems were observed because the SAMs modify the WF of ITO. However, the degrees of band bending occurring in these systems could not be attributed solely to the modified WFs of the substrate. This was apparent based on measurements of samples that included P3HT films prepared with different morphological structures. Changes in the morphological structure, due to different deposition methods and surface energies of the substrates, are necessarily connected to changes in the electronic structure, including changes in the electronic density of states (DOS), of P3HT. An association between (i) the WF differences between P3HT, ITO, and SAM/ITO substrates, (ii) the surface energies of the ITO and SAM/ITO substrates, which influence the morphology of the deposited P3HT layer, (iii) the DOS widths of P3HT, and (iv) the degree of band bending is suggested.
In situ, real-time polarized Raman spectroscopy was used to measure electrostatically induced carbon nanotube alignment in a polymer matrix. Discrete and reversible asymptotes of carbon nanotube G-band intensity were observed as a function of the applied electric field strength. It is proposed that as the electric field is increased, certain populations of carbon nanotubes attain sufficient alignment energy to overcome the randomizing thermal energy of the system. This is attributed to the electrostatic torque being a function of nanotube length, a relation that has been shown for dielectric rods and is extended here to carbon nanotubes. Nanotube batches of varying length distributions (hundreds of nanometers to micron-length) were created with different amounts of sonication energy. These distributions were quantified with atomic force microscopy measurements, and a model was developed relating these length distributions to the change in nanotube alignment at various electric field strengths. Nanotube polarizabilities determined from the model (α=10−30−10−32F⋅m2) were consistent with previously reported values. The effects of processing parameters such as sonication on the degree of achievable alignment as well as its implications are also discussed.
Traditional organolead-halide perovskite-based devices have shown rapid improvements in their power conversion efficiency in less than a decade, yet challenges remain for improving stability and film uniformity, as well as the elimination of lead to address toxicity issues. We fabricated lead-free methylammonium bismuth iodide (MBI) perovskite films and studied the effect of solvent annealing with dimethylformamide (DMF) on both (1) the crystallinity and structure of the films with X-ray diffraction and scanning electron microscopy and (2) the local optoelectronic properties of the films as measured via (photo)conductive atomic force microscopy. We found that solvent annealing leads to improved crystallinity and increased grain size in the MBI films as compared to the thermally annealed films. Furthermore, solvent-annealed MBI films show significantly increased electrical conductivity in the out-of-plane direction. Photoconductivity in both solvent-annealed and thermally annealed MBI films was increased in the grain interiors versus the grain boundaries. It was observed that DMF-induced solvent annealing impacts charge transport through the film, which can be a unique design parameter for optimizing local optoelectronic properties. By studying how solvent annealing affects the MBI film structure and changes the ways in which charges are transported through the film, we have developed a better understanding of how local optoelectronic properties are affected by DMF annealing.
ABSTRACTIn this work, poly(3‐hexylthiophene) (P3HT) films prepared using the matrix‐assisted pulsed laser evaporation (MAPLE) technique are shown to possess morphological structures that are dependent on molecular weight (MW). Specifically, the structures of low MW samples of MAPLE‐deposited film are composed of crystallites/aggregates embedded within highly disordered environments, whereas those of high MW samples are composed of aggregated domains connected by long polymer chains. Additionally, the crystallite size along the side‐chain (100) direction decreases, whereas the conjugation length increases with increasing molecular weight. This is qualitatively similar to the structure of spin‐cast films, though the MAPLE‐deposited films are more disordered. In‐plane carrier mobilities in the MAPLE‐deposited samples increase with MW, consistent with the notion that longer chains bridge adjacent aggregated domains thereby facilitating more effective charge transport. The carrier mobilities in the MAPLE‐deposited simples are consistently lower than those in the solvent‐cast samples for all molecular weights, consistent with the shorter conjugation length in samples prepared by this deposition technique. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018, 56, 652–662
Viscoelastic properties are central for gels and other materials. Simultaneously, high storage and loss moduli are difficult to attain due to their contrarian requirements to chemical structure. Biomimetic inorganic nanoparticles offer a promising toolbox for multiscale engineering of gel mechanics, but a conceptual framework for their molecular, nanoscale, mesoscale, and microscale engineering as viscoelastic materials is absent. Here we show nanoparticle gels with simultaneously high storage and loss moduli from CdTe nanoparticles. Viscoelastic figure of merit reaches 1.83 MPa exceeding that of comparable gels by 100–1000 times for glutathione-stabilized nanoparticles. The gels made from the smallest nanoparticles display the highest stiffness, which was attributed to the drastic change of GSH configurations when nanoparticles decrease in size. A computational model accounting for the difference in nanoparticle interactions for variable GSH configurations describes the unusual trends of nanoparticle gel viscoelasticity. These observations are generalizable to other NP gels interconnected by supramolecular interactions and lead to materials with high-load bearing abilities and energy dissipation needed for multiple technologies.