Characterization Of Transport Properties Research Articles

Nanoscale Simulation of Plastic Contaminants Migration in Packaging Materials and Potential Leaching into Model Food Fluids.

Polymers are the most commonly used packaging materials for nutrition and consumer products. The ever-growing concern over pollution and potential environmental contamination generated from single-use packaging materials has raised safety questions. Polymers used in these materials often contain impurities, including unreacted monomers and small oligomers. The characterization of transport properties, including diffusion and leaching of these molecules, is largely hampered by the long timescales involved in shelf life experiments. In this work, we employ atomistic molecular simulation techniques to explore the main mechanisms involved in the bulk and interfacial transport of monomer molecules from three polymers commonly employed as packaging materials: polyamide-6, polycarbonate, and poly(methyl methacrylate). Our simulations showed that both hopping and continuous diffusion play important roles in inbound monomer diffusion and that solvent-polymer compatibility significantly affects monomer leaching. These results provide rationalization for monomer leaching in model food formulations as well as bulky industry-relevant molecules. Through this molecular-scale characterization, we offer insights to aid in the design of polymer/consumer product interfaces with reduced risk of contamination and longer shelf life.

Combining linear-scaling quantum transport and machine-learning molecular dynamics to study thermal and electronic transports in complex materials

We propose an efficient approach for simultaneous prediction of thermal and electronic transport properties in complex materials. Firstly, a highly efficient machine-learned neuroevolution potential (NEP) is trained using reference data from quantum-mechanical density-functional theory calculations. This trained potential is then applied in large-scale molecular dynamics simulations, enabling the generation of realistic structures and accurate characterization of thermal transport properties. In addition, molecular dynamics simulations of atoms and linear-scaling quantum transport calculations of electrons are coupled to account for the electron-phonon scattering and other disorders that affect the charge carriers governing the electronic transport properties. We demonstrate the usefulness of this unified approach by studying electronic transport in pristine graphene and thermoelectric transport properties of a graphene antidot lattice, with a general-purpose NEP developed for carbon systems based on an extensive dataset.

Opto-electronic and thermoelectric properties of double perovskites Na2AgGaY6 (Y = Cl, Br, I) for energy conversion applications: DFT calculations

Double perovskites (DPs) that are both stable and environmentally sustainable are identified as an ideal choice for a broad range of applications, including thermoelectric and optoelectronic implementations. The current study investigates the complex physical characteristics of DPs Na2AgGaY6 (Y = Cl, Br, I) through the utilization of density functional theory (DFT), thus providing insights into its potential benefits in the fields of optoelectronics and thermal usage. The tolerance factor and Born’s stability criteria are meticulously calculated in order to determine the structural stability of the cubic phase. The calculated direct band gap values for Na2AgGaCl6 and Na2AgGaBr6 ensure maximum absorption in the visible and infrared spectra, respectively. Na2AgGaI6 is the most optimal DP used in photovoltaic devices. An examination has been conducted on the See-beck coefficient, electrical and thermal conductivities, and other essential parameters utilized in the characterization of transport properties. The compounds Na2AgGaI6, Na2AgGaBr6 and Na2AgGaCl6 demonstrate exceptional ZT indices of 0.78, 0.74 and 0.73, accordingly, emphasizing their critical importance in thermoelectric devices.

Model selection for dynamic interfacial tension of dead crude oil/brine to estimate pressure and temperature effects on the equilibrium tension

Interfacial tension (IFT) measurements using pendant drop techniques are typically time-dependent and embed the underlying physics that can be exploited. A physics-based modeling approach of the time-varying IFT is chosen to estimate the equilibrium IFT and to identify which phenomena are leading the dynamic. This approach is both consistent and reproducible, hence advantageous for routine research and industrial applications because typical approaches are especially challenging when the techniques rely on long-time measurements or detailed characterization of phase composition and transport properties. The approach is applied to the Brazilian pre-salt dead crude oil/brine system when the equilibrium between the phases and between bulk and interface concentrations are not assured initially. Selected models based on a different physical phenomenon, mainly focused on diffusion and sorption, and with a particular time scale behavior are tested on measured data. The model which better fits the data in its full-time range should point out which phenomenon is dominant. The results indicate that the model with t time scale seems preferable for this oil/brine system, which is associated with a diffusion-controlled process in multiple regimes, for instance, bulk-to-interface diffusion of naturally present interface chemicals and their rearrangement at the interface. The effect of pressure (14.7 psi–4000 psi) and temperature (22 °C–60 °C) variations on the equilibrium IFT of the Brazilian pre-salt reservoir dead crude oil/brine at various conditions is characterized and discussed using the consistent physics-based estimate for the equilibrium IFT. The results show that the equilibrium IFT does not change significantly with pressure and increases with temperature, further supporting the identified presence of naturally present interface chemicals in the transient IFT measurements and the brine ionic valence influence. Furthermore, the wettability of carbonate rock samples with different mineralogical compositions to the dead crude oil/formation water is assessed using adhesion tension which embeds both IFT and contact angle contributions. Pressure changes do not affect wettability considerably, while the effects of temperature increase show that every sample tended to be wetter to its respective fluid affinity, following the IFT temperature behavior.

Thermoelectric transport properties of Si, SiGe, and silicide CMOS-compatible thin films.

Characterization of thermoelectric transport properties for temperature sensing, cooling, and energy harvesting applications is necessary for a reliable device performance in progressively minimized computer chips. In this contribution, we present a fully automated thermovoltage and sheet resistance measurement setup, which is calibrated and tested for the production of silicon- and silicon-germanium-doped as well as silicide complementary metal-oxide-semiconductor-compatible thin films. A LabVIEW-programmed software application automatically controls the measurement and recording of thermovoltages at individually defined temperature set points. The setup maps average temperature and temperature differences simultaneously in the regime from 40 to 70 °C. The Seebeck coefficient calculated by means of the inversion method was used to eliminate the offset voltage influence. Finally, we present and discuss the Seebeck coefficient as well as the sheet resistance for application-specific different temperature set points of several doped poly-Si, poly-SiGe, and silicides.

Towards energy filtering in Mg2X-based composites: Investigating local carrier concentration and band alignment via SEM/EDX and transient Seebeck microprobe analysis

A comprehensive understanding of multi-phase materials requires the characterization of transport properties at the micro/nano-scale. Optimized alignments of the conduction bands and valence bands at the interfaces of multi-phase materials can enhance the properties of thermoelectric materials by filtering out undesired charge carriers and is a promising path towards high performance thermoelectric devices. Here, a micro-scale characterization technique using transient Seebeck microprobe analysis, scanning electron microscopy with energy-dispersive X-ray spectroscopy, and electronic transport modelling based on the Boltzmann transport equation modeling is introduced to assess the band diagram and estimate the band offset in multi-phase materials. This characterization technique is applied to a composite of magnesium silicide-based materials. This material class is prone to form self-assembling nano-structured composites driven by a miscibility gap in the solid solutions series. Our analysis reveals changes in carrier concentration upon composite formation and considerable band offsets for both conduction and valence band when synthesizing nominally undoped composites. Employing Bi as dopant we show that Bi exhibits a preference for the Sn-rich phase, changing the carrier concentration differently in the Sn-rich matrix phase compared to the Si-rich secondary phase, effectively altering the band alignment of the composite. This demonstrates that our approach can be utilized to measure and manipulate the band offset within the composite to achieve optimal thermoelectric performance.

Thermal Conductivity of 3C/4H-SiC Nanowires by Molecular Dynamics Simulation.

Silicon carbide (SiC) is a promising material for thermoelectric power generation. The characterization of thermal transport properties is essential to understanding their applications in thermoelectric devices. The existence of stacking faults, which originate from the "wrong" stacking sequences of Si-C bilayers, is a general feature of SiC. However, the effects of stacking faults on the thermal properties of SiC are not well understood. In this study, we evaluated the accuracy of Tersoff, MEAM, and GW potentials in describing the thermal transport of SiC. Additionally, the thermal conductivity of 3C/4H-SiC nanowires was investigated using non-equilibrium molecular dynamics simulations (NEMD). Our results show that thermal conductivity exhibits an increase and then saturation as the total lengths of the 3C/4H-SiC nanowires vary from 23.9 nm to 95.6 nm, showing the size effect of molecular dynamics simulations of the thermal conductivity. There is a minimum thermal conductivity, as a function of uniform period length, of the 3C/4H-SiC nanowires. However, the thermal conductivities of nanowires weakly depend on the gradient period lengths and the ratio of 3C/4H. Additionally, the thermal conductivity of 3C/4H-SiC nanowires decreases continuously from compressive strain to tensile strain. The reduction in thermal conductivity suggests that 3C/4H-SiC nanowires have potential applications in advanced thermoelectric devices. Our study provides insights into the thermal transport properties of SiC nanowires and can guide the development of SiC-based thermoelectric materials.

Thermo-economic performance limit analysis of combined heat and power systems for optimal working fluid selections

In previous works, we have proposed the thermodynamic performance limit analysis methodology for the organic Rankine cycle for analyzing the impact of working fluid properties on system performance. Here the concept is extended to the thermo-economic performance limits, and is applied to a combined heat and power system based on an organic Rankine cycle. Working fluids are characterized with 8 characteristic thermodynamic and transport properties based on a corresponding state model and a residual entropy scaling approach. The 8 fluid characteristic properties along with 3 system operational parameters are optimized using a multi-objective genetic algorithm; a Monte Carlo algorithm is further adopted to avoid sub-optimal convergences. As the result, the performance limits could be well represented by the trade-off (Pareto front) between the maximized thermal efficiency and minimized payback period. The impact of the fluid characteristic properties on both thermodynamic and economic targets is investigated and ultimately guided the choice of working fluids: low molar mass, low thermal conductivity scaling factor, high viscosity scaling factor and high critical pressure are always preferred. "Wet" working fluid is preferred for a high thermal efficiency while "dry" working fluid is favored for a short payback period. Critical temperature has the most profound impact, while ideal gas isobaric heat capacity and acentric factor have negligible impacts. The choice of working fluid, system design (e.g., recuperative effectiveness) and system operational parameters (e.g., evaporation temperature) highly depends on the given hot sources and the preferences to the thermodynamic and economic targets.

GaSb band-structure models for electron density determinations from Raman measurements.

We investigate the use of Raman spectroscopy to measure carrier concentrations in GaSb epilayers to aid in the development of this technique for the nondestructive characterization of transport properties in doped semiconductors. The carrier concentration is quantified by modeling the measured coupled optical phonon-free carrier plasmon mode spectra. We employ the Lindhard-Mermin optical susceptibility model with contributions from carriers in the two lowest GaSb conduction-band minima, the and minima. Furthermore, we evaluate three conduction-band models: (1) both minima parabolic and isotropic, (2) the minimum non-parabolic and isotropic and the minima parabolic and isotropic, and (3) the minimum non-parabolic and isotropic and the minima parabolic and ellipsoidal. For a given epilayer, the carrier concentration determined from the spectral simulations was consistently higher for the ellipsoidal minima model than the other two models. To evaluate the conduction-band models, we calculated the to electron mobility ratio necessary for the electron concentrations from the Raman spectral measurements to reproduce those from the Hall effect measurements. We found that the model with the ellipsoidal minima agreed best with reported carrier-dependent mobility-ratio values. Hence, employing isotropic minima in GaSb conduction-band models, a common assumption when describing the GaSb conduction band, likely results in an underestimation of carrier concentration at room temperature and higher doping levels. This observation could have implications for Raman spectral modeling and any investigation involving the GaSb conduction band, e.g., modeling electrical measurements or calculating electron mobility.

Hierarchical reconstruction of 3D well-connected porous media from 2D exemplars using statistics-informed neural network

The relationships between porous microstructures and transport properties are of fundamental importance in various scientific and engineering applications. Due to the intricacy, stochasticity and heterogeneity of porous media, reliable characterization and modeling of transport properties often require a complete dataset of internal microstructure samples. However, it is often an unbearable cost to acquire sufficient 3D digital microstructures by purely using microscopic imaging systems. This paper presents a machine learning-based technique to hierarchically reconstruct 3D well-connected porous microstructures from one isotropic or several anisotropic low-cost 2D exemplar(s). To compactly characterize the large-scale microstructural features, a Gaussian image pyramid is built for each 2D exemplar. Local morphology patterns are collected from the Gaussian image pyramids, and then they serve as the training data to embed the 2D morphological statistics into feed-forward neural networks at multiple length levels. By using a specially-developed morphology integration scheme, the 3D morphological statistics at different levels can be inferred from the statistics-informed neural networks. Gibbs sampling is adopted to hierarchically reconstruct 3D microstructures by using multi-level 3D morphological statistics, where the large-scale, regional and local morphological patterns are statistically generated and successively added to the same 3D random field. The proposed method is tested on a series of porous media with distinct morphologies, and the statistical equivalence between the reconstructed and the real microstructures is systematically evaluated by comparing morphological descriptors and transport properties. The results demonstrate that the proposed 2D-to-3D microstructure reconstruction method is a universal and efficient approach to generating morphologically and physically realistic samples of porous media.

Comprehensive characterization of gas diffusion through graphene oxide membranes

Graphene oxide (GO) based multi-layered membranes have shown outstanding molecular-sieving properties for gas separation, surpassing the upper bound for polymeric membranes especially for hydrogen decarbonization. At the same time, the mechanism of gas permeation through such 2D GO membranes is very different in comparison to the traditional polymeric membranes due to multilayer, laminated nature of the former. For strategical design of novel membranes based on two-dimensional materials, it is important to understand the mechanism and to be able to measure two key parameters for gas transport: diffusivity and solubility. Such measurements are well established for the characterization of transport properties of bulk polymeric membranes. However, it is still a challenge to measure gas diffusion coefficients directly and accurately in ultra-thin multi-layered membranes. The lack of characterization limits our understanding of the mechanisms of gas transport though such membranes. In this work, we applied a time-lag method to determine the diffusivities for He, H2, O2, N2, CH4, CO2 and H2/CO2 equimolar mixture by on-line mass spectrometry. In contrast to polymeric membranes, the diffusivity and diffusion activation energy for all gases in 2D membranes are exponentially dependent on pathway length. Thus, in 2D membrane we can use an easy strategy to precisely regulate permeability and selectivity by the adjustment of the number of nanolayers and the size of 2D flakes, which is not possible using traditional polymeric membranes. This study is important for both the characterization and the standardization of gas transport properties of multi-layered membranes, and the design of novel membranes based on 2D materials.

Characterization of Electronic Transport Properties of Narrow-Band Gap Fe(Se1-xTex)2 Alloys via the Two-Band Model

Environmentally sustainable thermoelectric technologies can be more broadly applied in industries once the performance of thermoelectric materials is improved. Several approaches have been proposed to improve the electronic transport properties of thermoelectric materials. The effects of each approach on the electronic properties can be evaluated by changes in the band parameters. The Single Parabolic Band (SPB) model has been widely used to determine the effect of different materials engineering strategies on band parameters, such as the density-of-states effective mass and deformation potential. However, when the material has a narrow band gap, the Two-Band (TB) model better describes the changes in band parameters, as it includes the bipolar conduction from the minority carrier band. Here, the band parameters of previously reported Fe(Se1-xTex)2 (x/i> = 0, 0.2, 0.6, 0.8, 1) alloys, whose band gap significantly decreases with x/i>, have been estimated using the SPB and TB models. While the x-dependent band parameters obtained via the SPB model varied abruptly with x/i>, all the band parameters estimated by the TB model changed linearly with x/i>. The abruptness observed in the band parameters of the SPB model can be attributed to artifacts reflected in the single band, which occurs when the minority carrier band and band gap change are not included. The bipolar thermal conductivity of Fe(Se1-xTex)2 alloys was also calculated using the TB model, and is understood in terms of changes in the weighted mobility ratio, Hall carrier concentration, and band gap in terms of alloy composition, x/i>.

Quantum Hall effect systems of electrons with anisotropic patterns

An almost ideal two-dimensional system of electrons can now be easily created in semiconductor heterojunctions. The quantum Hall effect state of the electrons is induced via the application of a strong perpendicular magnetic under specific quantum conditions. The most robust integer and/or fractional quantum Hall states already observed show the expected characteristic magnetoresistance for such systems. However, anisotropic patterns and features in transport properties have been seen for a few other peculiar cases. The origin of such anisotropic patterns may have various mechanisms or may also be due the specific details of the system and material such as the isotropic or anisotropic nature of the effective mass of electrons, the nature of the host substrate parameters, the nature of the interaction potentials, as well as other subtler effects. The interplay between all these factors can lead to many outcomes. In this work we consider small quantum Hall states of electrons at filling factor 1/6 and study the appearance of such anisotropic patterns as a result of some form of innate interaction anisotropy in the system.

A guide for the characterization of organic electrochemical transistors and channel materials.

The organic electrochemical transistor (OECT) is one of the most versatile devices within the bioelectronics toolbox, with its compatibility with aqueous media and the ability to transduce and amplify ionic and biological signals into an electronic output. The OECT operation relies on the mixed (ionic and electronic charge) conduction properties of the material in its channel. With the increased popularity of OECTs in bioelectronics applications and to benchmark mixed conduction properties of channel materials, the characterization methods have broadened somewhat heterogeneously. We intend this review to be a guide for the characterization methods of the OECT and the channel materials used. Our review is composed of two main sections. First, we review techniques to fabricate the OECT, introduce different form factors and configurations, and describe the device operation principle. We then discuss the OECT performance figures of merit and detail the experimental procedures to obtain these characteristics. In the second section, we shed light on the characterization of mixed transport properties of channel materials and describe how to assess films' interactions with aqueous electrolytes. In particular, we introduce experimental methods to monitor ion motion and diffusion, charge carrier mobility, and water uptake in the films. We also discuss a few theoretical models describing ion-polymer interactions. We hope that the guidelines we bring together in this review will help researchers perform a more comprehensive and consistent comparison of new materials and device designs, and they will be used to identify advances and opportunities to improve the device performance, progressing the field of organic bioelectronics.

Quantitative Characterization of Transport Properties in Roller-Compacted Concrete by Incorporating RCPT and TDR

Quantitative Characterization of Transport Properties in Roller-Compacted Concrete by Incorporating RCPT and TDR

Full Characterization of Water Transport Properties in Polyetherketoneketone (PEKK)

Full Characterization of Water Transport Properties in Polyetherketoneketone (PEKK)

Noninvasive thermal sensors measure skin physiology

Sensing technology provides quantitative characterization of blood flow, hydration, perfusion, skin temperature, and thermal transport properties.

Effects of electron- and hole-current hysteresis on trap characterization in organo-inorganic halide perovskite

Charge trap density and carrier mobility of perovskite materials are the critical properties of perovskite solar cells. The space charge limited current (SCLC) method, which measures a dark current–voltage (I-V) curve of a single-carrier device has found extensive use for studying the trap density and charge carrier mobility in perovskite materials. Herein, it was found that the electron- and hole-current in organo-lead perovskite-based single-carrier device undergoes significant hysteresis under forward and reverse scanning due to the mobile ions. In addition, it was also observed that measuring history has a detrimental effect on hysteresis resulting in possible overestimation or underestimation of the extracted electrical values from the SCLC measurement. In the forward/reverse scanning process, the mobile ionic defects enhance/shield the charge in the traps due to ionic charging/discharging, thereby increasing/reducing the interface barrier and net charge in the I-V scanning, which in turn affects the determination of transport properties of the carrier. These results raise quite a few doubts over the direct application of classical SCLC measurements for the accurate characterization of intrinsic transport properties of the mixed ionic-electronic perovskite.

The Role of Ion-Correlation in Reducing the Lithium Transference Number in Lithium-Ion Polyelectrolyte Solutions

Non-aqueous polyelectrolyte solutions (PESs) have been suggested as a promising route to high conductivity, high transference number (t+) electrolytes.1–3 State-of-the-art liquid electrolytes suffer from low t+, meaning the majority of ionic conductivity results from motion of the anion rather than the electrochemically active Li+ ion. Increasing t+ requires decreasing the mobility of the anion, which is dictated by both the diffusion of the anion as well as its net charge. PESs are intuitively appealing because anchoring the anion to a polymer backbone slows down the motion of the electrochemically inactive anion while maintaining higher ion conductivity through improved ion dissociation and solvent-mediated Li+ transport. However, in polyelectrolyte systems, increasing molecular weight both decreases polymer diffusion and increases charge, which will act as competing effects for t+.Recent molecular dynamic simulations of PESs have highlighted the critical importance of correlated ion motion in these systems and have called into question oligomeric PESs as a feasible strategy to achieving high t+ and conductivity electrolytes4,5 In this work we discuss complete studies of transport properties in lithium-ion and lithium metal battery-relevant PESs- specifically lithium triflimide appended polystyrene (PS-LiTFSI) and polymethacrylate (PM-LiTFSI) dissolved in carbonate blends. All prior PES experimental work in the literature has relied on ideal solution assumptions for measuring transport properties. This work represents the first rigorous characterization of transport properties for a battery-relevant polyelectrolyte solution. Using electrophoretic NMR and electrochemical experiments, we characterized the transport properties, including the electrophoretic ion mobilities, conductivity, diffusion coefficients, and t+ of these model PESs. While previous studies that rely on ideal assumptions predict that PESs will have higher t+ than monomeric solutions, we demonstrate that below the entanglement limit, t+ decreases with increasing degree of polymerization. For higher degrees of polymerization, we directly observe Li+ move in the “wrong direction” in an electric field, evidence of a negative transference number due to correlated motion through ion clustering. Using calculated Onsager transport coefficients and insights from molecular dynamics modeling, we demonstrate that despite selectively slowing anion motion using polyanions, anion-anion correlation through the polymer backbone and cation-anion correlation through ion aggregates reduce the t+ in non-entangled PESs.References Diederichsen, K. M. et al. ACS Energy Lett. (2017).Diederichsen, K. M. et al. Macromolecules (2018).Dewing, B. L., et al. Chem. Mater. (2020).Fong, K. D. et al. ACS Cent. Sci. (2019).Fong, K. D., et al. Macromolecules (2020).

Effect of nonequilibrium order parameter on the optical response of superconductor Sr2RuO4

The breaking of time reversal symmetry of the superconducting pairings is expected to manifest itself through characteristic transport properties such as a non-zero Kerr angle which provides fingerprint of the quantum anomalous Hall state. In this work, we theoretically study the Kerr effect or the Hall-type response and also consider how this response is modified by the nonequilibrium shape of order parameter of the superconducting state due to the influence of the electromagnetic radiation for the most favorable candidates of chiral superconducting order parameters and of the non-chiral states in strontium ruthenate (Sr2RuO4). The unique sensitivity of the Hall-type response introduced above to different types of pairings can be used to identify the most favored pairing which is a serious doubt on the superconducting state of this material.