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At least 37 records · Page 2

Decoupling relationship between economic output and carbon emission in the Chinese construction industry

By positioning in the discourse that economic output is always coupled with natural resource depletion, pollution, and carbon emission, decoupling analysis is widely adopted to evaluate how “quality” economic growth can lead to fewer such downsides so as to encourage sustainable development. This paper aims at examining the decoupling relationship between economic output and carbon emission by focusing on China's construction industry, which is a pillar industry for national economic growth, meanwhile contributes a huge amount of carbon emission. The method of Tapio decoupling model is used to examine the decoupling relationships at both national and provincial levels from 2005 to 2015. It continues to identify the driving force leading to a certain decoupling state by adopting the logarithmic mean Divisia index (LMDI). Results show that: (1) there existed an expansive decoupling relationship between economic growth and construction carbon emission in most provinces of China during 2005–2015; (2) Shanghai presented the best decoupling performance, while in contrast, other provinces such as Guizhou and Fujian displayed expansive negative decoupling state; and (3) “Economic output” played the most significant role in inhibiting the decoupling at both national and provincial levels, while “Indirect carbon intensity” was the main driver for promoting the national decoupling. Although the paper refers to the specific construction of China, the decoupling analysis approach can be extended to other countries as well as to other pollutants such as land pollution, waste water and haze. The understanding of driving forces for the decoupling state in China's construction industry provides international policy-makers with valuable reference for formulating effective measures to balance the dilemma between economic output and carbon emission.

54 ENVIRONMENTAL SCIENCES↗

A unified heteronuclear decoupling strategy for magic-angle-spinning solid-state NMR spectroscopy

A unified strategy of two-pulse based heteronuclear decoupling for solid-state magic-angle spinning nuclear magnetic resonance is presented. The analysis presented here shows that different decoupling sequences like two-pulse phase-modulation (TPPM), X-inverse-X (XiX), and finite pulse refocused continuous wave (rCW{sup A}) are basically specific solutions of a more generalized decoupling scheme which incorporates the concept of time-modulation along with phase-modulation. A plethora of other good decoupling conditions apart from the standard, TPPM, XiX, and rCW{sup A} decoupling conditions are available from the unified decoupling approach. The importance of combined time- and phase-modulation in order to achieve the best decoupling conditions is delineated. The consequences of different indirect dipolar interactions arising from cross terms comprising of heteronuclear and homonuclear dipolar coupling terms and also those between heteronuclear dipolar coupling and chemical-shift anisotropy terms are presented in order to unfold the effects of anisotropic interactions under different decoupling conditions. Extensive numerical simulation results are corroborated with experiments on standard amino acids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Distribution of U.S. Electric Utility Revenue Decoupling Rate Impacts from 2005 to 2017

Investments in energy efficiency and distributed generation reduce electric utility retail sales. Since electric utilities have historically collected a large portion of revenues from volumetric energy rates (¢/kWh), such reductions in sales can impact the utility’s ability to sufficiently recover non-production costs. Regulatory mechanisms that “decouple” utility revenues from sales were implemented to help make the utility indifferent to energy efficiency and distributed generation by ensuring the utility is able to collect an allowed level of revenue each year regardless of its sales. However, noticeable and consistent surcharges over time may create the perception of an incorrectly designed or implemented decoupling mechanism. To date, there are limited quantitative analyses of the rate adjustments due to decoupling mechanisms implemented among U.S. electric utilities (see Morgan, 2013). Given the recent rapid increase in distributed energy resource (DER) adoption in some states and utility service territories, consumers may be facing more prevalent and ongoing decoupling surcharges. This, in turn, may undermine stakeholder support for implementation of decoupling mechanisms and the associated utility support for energy efficiency and DERs. To determine the size of retail rate adjustments associated with decoupling mechanisms and whether they have a tendency towards bill surcharges or credits, we analyzed a large dataset of historical annual decoupling rate adjustments for 21 electric utilities in 11 states between 2005 and 2017. We found that decoupling mechanisms adjusted rates, both up and down, between rate cases, and the majority of those adjustments (54 percent) are small (within a range of -1 to 1 percent). However, we also found that 64 percent of the rate adjustment observations in our sample showed a positive rate adjustment. Importantly, once a surcharge is applied there is an 86 percent chance that there will be a surcharge in the next year as well. While our analysis did not seek to understand the root causes for such results, some possible factors include the accuracy of revenue requirement forecasts, emerging structural changes in customer use and production of energy, misaligned financial motivation, and other factors that influence sales (e.g., economic recession).

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Investigation of the marine boundary layer cloud and CCN properties under coupled and decoupled conditions over the Azores

Here, six coupled and decoupled marine boundary layer (MBL) clouds were chosen from the 19 month Atmospheric Radiation Measurement Mobile Facility data set over the Azores. Thresholds of liquid water potential temperature difference Δθ L < 0.5 K (>0.5 K) and total water mixing ratio difference Δq t < 0.5 g/kg (>0.5 g/kg) below the cloud base were used for selecting the coupled (decoupled) cases. A schematic diagram was given to demonstrate the coupled and decoupled MBL vertical structures and how they associate with nondrizzle, virga, and rain drizzle events. Out of a total of 2676 5 min samples, 34.5% were classified as coupled and 65.5% as decoupled, 36.2% as nondrizzle and 63.8% as drizzle (47.7% as virga and 16.1% as rain), and 33.4% as daytime and 66.6% as nighttime. The decoupled cloud layer is deeper (0.406 km) than coupled cloud layer (0.304 km), and its liquid water path and cloud droplet effective radius (r e ) values (122.1 gm -2 and 13.0 µm) are higher than coupled ones (83.7 gm -2 and 10.4 µm). Conversely, decoupled stratocumuli have lower cloud droplet number concentration (N d ) and surface cloud condensation nucleus (CCN) concentration (N CCN ) (74.5 cm -3 and 150.9 cm -3 ) than coupled stratocumuli (111.7 cm -3 and 216.4 cm -3 ). The linear regressions between r e and N d with N CCN have demonstrated that coupled r e and N d strongly depend on N CCN and have higher correlations (-0.56 and 0.59) with N CCN than decoupled results (-0.14 and 0.25). The MBL cloud properties under nondrizzle and virga drizzle conditions are similar to each other but significantly different to those of rain drizzle.

54 ENVIRONMENTAL SCIENCES↗

Estimating the Decoupling Degree of Subtropical Marine Stratocumulus Decks From Satellite

The decoupling degree of stratocumulus (Sc) decks is an important quantity dictating evolutions of Sc. In subtropical oceans, the Sc decoupling is a key intermediate process of the Sc-to-cumulus transitions, a persistent phenomenon that is not fully understood. This study introduces a new approach for estimating the degree of decoupling of subtropical Sc decks using passive satellite sensors. This method is limited to regions where Sc decks are advected over progressively warmer water. This is most common in the subtropics. The estimation concept is that decoupled Sc clouds under cold-advection conditions are fed by spreading of the tops of cumulus clouds that are coupled. The cumulus clouds constitute a much larger liquid water path over small areas, which is identified by a positive skewness of the liquid water path, a quantity measurable from high-resolution satellite data. The decoupling degree here is defined as the difference between the Sc cloud-base height and lifting condensation level that is the cumulus cloud-base height under cold-advection conditions. This concept and the satellite-based estimations are supported by ship measurements over the Northeast Pacific. One-year climatology of the satellite-inferred decoupling degree was generated over the same region, revealing a coherent pattern of offshore decoupling, consistent with previous theory and field-campaign observations.

54 ENVIRONMENTAL SCIENCES↗

Episodes of Warm-Air Advection Causing Cloud-Surface Decoupling During the MARCUS

It has been understood for decades that advection of a cloud-topped marine boundary layer (CTBL) over warmer sea surface causes the stratification (or decoupling) of the CTBL via the entrainment feedback, a mechanism commonly known as “deepening-warming” decoupling that is typical in subtropics. This study focuses on the opposite direction of advection, that is, low-level warm air advection (LLWAA), and its impacts on the decoupling degree of a CTBL. Our hypothesis is that LLWAA stabilizes a CTBL, causing a decoupling of the CTBL. It is tested for three LLWAA episodes observed during the Measurements of Aerosols, Radiation, and CloUds over the Southern Ocean (MARCUS) field campaign between the Hobart (43°S, 147°E), Australia, and several Antarctic coast stations. By synthesizing the shipborne measurements of CTBL structure, Himawari-8 satellite imagery of cloud fields, and reanalysis of meteorological field, four common characteristics of CTBLs under the LLWAA are found: (1) CTBLs are highly stratified to the extent that penetrations of cumulus into main temperature inversions, which are common for subtropical decoupled CTBLs, do not exist; (2) sea surface temperature is 1–2 K lower than the near-surface air temperature; (3) clouds manifest stratiform with lifetime as long as several tens of hours; and (4) they locate in warm sectors of middle-latitude cyclones. Possible mechanisms for the maintenance of decoupled clouds under LLWAA are discussed in terms of dynamic and thermodynamic factors. Lapse rates of the decoupled CTBLs are markedly lower than those commonly used for passive satellite estimation of cloud top heights.

54 ENVIRONMENTAL SCIENCES↗

Thermodynamics conditions of matter in the neutrino decoupling region during neutron star mergers

In this work we investigate the thermodynamics conditions at which neutrinos decouple from matter in neutron star merger remnants by post-processing results of merger simulations. We find that the matter density and the neutrino energies are the most relevant quantities in determining the decoupling surface location. For mean energy neutrinos (~9, 15 and 24 MeV for ν e , $\bar{ν}$ e and ν μ,τ , respectively) the transition between diffusion and free-streaming conditions occurs around 10 11 g cm -3 for all neutrino species. Weak and thermal equilibrium freeze-out occurs deeper (several 10 12 g cm -3 ) for heavy-flavor neutrinos than for $\bar{ν}$ e and ν e (≳10 11 g cm -3 ). Decoupling temperatures are broadly in agreement with the average neutrino energies, with softer equations of state characterized by ~1 MeV larger decoupling temperatures. Neutrinos streaming at infinity with different energies come from different remnant parts. While low-energy neutrinos (~3 MeV) decouple at ρ~10 13 g cm -3 , T~10 MeV and Y e ≲0.1 close to weak equilibrium, high-energy ones (~50 MeV ) decouple from the disk at ρ~10 9 g cm -3 , T~2 MeV and Y e ≳0.25. The presence of a massive NS or a BH influences the neutrino thermalization. While in the former case decoupling surfaces are present for all relevant energies, the lower maximum density ( ≲10 12 g cm -3 ) in BH-torus systems does not allow softer neutrinos to thermalize and diffuse.

79 ASTRONOMY AND ASTROPHYSICS↗

Supply voltage decoupling circuits for voltage droop mitigation

Circuits and methods are provided for utilizing decoupling capacitors to mitigate voltage droop on power supply lines of a power distribution network. A power supply line is capacitively decoupled using a first decoupling capacitor connected to the power supply line and charged to a first voltage level of the power supply line. A second decoupling capacitor is pre-charged to a second voltage level greater than the first voltage level and held in standby. A control circuit determines or predicts an occurrence of a droop event in which the first voltage decreases to a level which is at or below a droop threshold voltage level, and selectively connects the pre-charged second decoupling capacitor to the power supply line to source additional boosting current through discharging of the second decoupling capacitor and thereby capacitively decouple the power supply line using the higher second voltage and additional boosting current.

Zhang, Xin↗

Marine Boundary Layer Decoupling and the Stable Isotopic Composition of Water Vapor

Decoupling of the subcloud layer in stratocumulus-topped marine boundary layers (STMBL) influences low-cloud cover by limiting the supply of water vapor from the surface. However, the relative importance of mixing between surface fluxes and other reservoirs of water vapor as a function of the degree of decoupling is poorly understood. Water vapor transport within the STMBL and its response to decoupling is explored using surface measurements of water vapor isotopic composition that were obtained from Graciosa Island, Azores, during the summer and fall of 2018. The data show an inverse relationship between the decoupling metric, Δq, and the degree of drying from an isotopically depleted water vapor source. The isotopic data require some degree of drying with an isotopically depleted source for coupled conditions, and likely require a small amount of mixing even for strongly decoupled conditions. The data are consistent with mixing between purely local reservoirs of water vapor, subjected to a small amount of condensation and fractionation, and do not require the invocation of large-scale transport of water vapor aloft or additional cloud-formation effects aloft.

54 ENVIRONMENTAL SCIENCES↗

Idealized Large-Eddy Simulations of Stratocumulus Advecting over Cold Water. Part I: Boundary Layer Decoupling

Abstract We explore the decoupling physics of a stratocumulus-topped boundary layer (STBL) moving over cooler water, a situation mimicking warm-air advection (WADV). We simulate an initially well-mixed STBL over a doubly periodic domain with the sea surface temperature decreasing linearly over time using the System for Atmospheric Modeling large-eddy model. Due to the surface cooling, the STBL becomes increasingly stably stratified, manifested as a near-surface temperature inversion topped by a well-mixed cloud-containing layer. Unlike the stably stratified STBL in cold-air advection (CADV) that is characterized by cumulus coupling, the stratocumulus deck in the WADV is unambiguously decoupled from the sea surface, manifested as weakly negative buoyancy flux throughout the subcloud layer. Without the influxes of buoyancy from the surface, the convective circulation in the well-mixed cloud-containing layer is driven by cloud-top radiative cooling. In such a regime, the downdrafts propel the circulation, in contrast to that in CADV regime for which the cumulus updrafts play a more determinant role. Such a contrast in convection regime explains the difference in many aspects of the STBLs including the entrainment rate, cloud homogeneity, vertical exchanges of heat and moisture, and lifetime of the stratocumulus deck, with the last being subject to a more thorough investigation in Part II. Finally, we investigate under what conditions a secondary stratus near the surface (or fog) can form in the WADV. We found that weaker subsidence favors the formation of fog whereas a more rapid surface cooling rate does not. Significant Statement The low-lying blanketlike clouds, called stratocumulus (Sc), reflect much incoming sunlight, substantially modulating Earth’s temperature. While much is known about how the Sc evolves when it moves over warmer water, few studies examine the opposite situation of Sc moving over colder water. We used a high-resolution numerical model to simulate such a case. When moving over cold water, the Sc becomes unambiguously decoupled from the water surface, distinctive from its warm counterpart in which the Sc interacts with the water surface via intermittent cauliflower-like clouds called cumulus clouds. Such decoupling influences many aspects of the Sc–sea surface system, which combine to alter the ability of the Sc to reflect sunlight, thereby influencing the climate. This work laid the foundation for future work that quantifies the contribution of such a decoupled Sc regime to Earth’s radiative budget and climate change.

54 ENVIRONMENTAL SCIENCES↗

Examining the evidence for decoupling between photosynthesis and transpiration during heat extremes

Recent experimental evidence suggests that during heat extremes, wooded ecosystems may decouple photosynthesis and transpiration, reducing photosynthesis to near zero but increasing transpiration into the boundary layer. This feedback may act to dampen, rather than amplify, heat extremes in wooded ecosystems. We examined eddy covariance databases (OzFlux and FLUXNET2015) to identify whether there was field-based evidence to support these experimental findings. We focused on two types of heat extremes: (i) the 3 days leading up to a temperature extreme, defined as including a daily maximum temperature >37 ° C (similar to the widely used TXx metric), and (ii) heatwaves, defined as 3 or more consecutive days above 35 ° C. When focusing on (i), we found some evidence of reduced photosynthesis and sustained or increased latent heat fluxes at seven Australian evergreen wooded flux sites. However, when considering the role of vapour pressure deficit and focusing on (ii), we were unable to conclusively disentangle the decoupling between photosynthesis and latent heat flux from the effect of increasing the vapour pressure deficit. Outside of Australia, the Tier-1 FLUXNET2015 database provided limited scope to tackle this issue as it does not sample sufficient high temperature events with which to probe the physiological response of trees to extreme heat. Thus, further work is required to determine whether this photosynthetic decoupling occurs widely, ideally by matching experimental species with those found at eddy covariance tower sites. Such measurements would allow this decoupling mechanism to be probed experimentally and at the ecosystem scale. Transpiration during heatwaves remains a key issue to resolve, as no land surface model includes a decoupling mechanism, and any potential dampening of the land–atmosphere amplification is thus not included in climate model projections.

54 ENVIRONMENTAL SCIENCES↗

Decoupling of ion conductivity from segmental dynamics in oligomeric ethylene oxide functionalized oxanorbornene dicarboximide homopolymers

Here, in order to design more effective solid polymer electrolytes, it is important to decouple ion conductivityfrom polymer segmental motion. To that end, novel polymers based on oxanorbornene dicarboximidemonomers with varying lengths of oligomeric ethylene oxide side chains have been synthesized usingring opening metathesis polymerization. These unique polymers have a fairly rigid and bulky backboneand were used to investigate the decoupling of ion motion from polymer segmental dynamics. Ionconductivity was measured using broadband dielectric spectroscopy for varying levels of added lithiumsalt. The conductivity data demonstrate six to seven orders of separation in timescale of ion conductivityfrom polymer segmental motion for polymers with shorter ethylene oxide side chains. However,commensurate changes in the glass transition temperatures T g reduce the effect of decoupling in ionconductivity and lead to lower conductivity at ambient conditions. These results suggest that both anincrease in decoupling and a reduction in T g might be required to develop solid polymer electrolytes withhigh ion conductivity at room temperature.

36 MATERIALS SCIENCE↗

HST IMAGING OF DUST STRUCTURES AND STARS IN THE RAM PRESSURE STRIPPED VIRGO SPIRALS NGC 4402 AND NGC 4522: STRIPPED FROM THE OUTSIDE IN WITH DENSE CLOUD DECOUPLING

We describe and constrain the origins of interstellar medium (ISM) structures likely created by ongoing intracluster medium (ICM) ram pressure stripping in two Virgo Cluster spirals, NGC 4522 and NGC 4402, using Hubble Space Telescope (HST) BVI images of dust extinction and stars, as well as supplementary H i, H α , and radio continuum images. With a spatial resolution of ∼10 pc in the HST images, this is the highest-resolution study to date of the physical processes that occur during an ICM–ISM ram pressure stripping interaction, ram pressure stripping's effects on the multi-phase, multi-density ISM, and the formation and evolution of ram-pressure-stripped tails. In dust extinction, we view the leading side of NGC 4402 and the trailing side of NGC 4522, and so we see distinct types of features in both. In both galaxies, we identify some regions where dense clouds are decoupling or have decoupled and others where it appears that kiloparsec-sized sections of the ISM are moving coherently. NGC 4522 has experienced stronger, more recent pressure and has the “jellyfish” morphology characteristic of some ram-pressure-stripped galaxies. Its stripped tail extends up from the disk plane in continuous upturns of dust and stars curving up to ∼2 kpc above the disk plane. On the other side of the galaxy, there is a kinematically and morphologically distinct extraplanar arm of young, blue stars and ISM above a mostly stripped portion of the disk, and between it and the disk plane are decoupled dust clouds that have not been completely stripped. The leading side of NGC 4402 contains two kiloparsec-scale linear dust filaments with complex substructure that have partially decoupled from the surrounding ISM. NGC 4402 also contains long dust ridges, suggesting that large parts of the ISM are being pushed out at once. Both galaxies contain long ridges of polarized radio continuum emission indicating the presence of large-scale, ordered magnetic fields. We propose that magnetic fields could bind together gas of different densities, causing nearby gas of different densities to be stripped at the same rate and creating the large, coherent dust ridges and upturns. A number of factors likely play roles in determining what types of structures form as a result of ram pressure, including ram pressure strength and history, the location within the galaxy relative to the leading side, and pre-existing substructure in the ISM that may be bound together by magnetic fields during stripping.

79 ASTRONOMY AND ASTROPHYSICS↗

Design and optimization of flexible decoupled high-temperature gas-cooled reactor plants with thermal energy storage

Advanced nuclear power plants are well-positioned for future zero-carbon grids, however, the need for flexible power generation will be required over the traditional emphasis on baseload generation for meeting historical demands. To achieve such flexibility, this work examines viable configurations for coupling nuclear energy production with thermal energy storage. Previous designs on nuclear-thermal energy storage configurations for advanced reactor designs, which utilized reactor steam as the heat source for charging the thermal energy storage, are restricted by the heat diversion ratio and efficiency losses, thus their impacts can be limited. In this context, this study proposes configurations for fully decoupling the nuclear reactor from the power cycle and positioning the storage as an intermediate loop, thereby achieving an unconstrained heat diversion ratio and improved efficiency. Compared with a standard high-temperature gas-cooled reactor’s power cycle, steady-state thermodynamic modeling and dispatch optimizations quantify the benefits of a steam reheat cycle within the fully decoupled thermal energy system to separate the plant cycle from the high-pressure primary side. These benefits are further detailed, compatible with required high-temperature and high-pressure conditions, through (1) open-source dynamic transient models that examine the impact of off-design operation on the systems, (2) the investigation of components design and costing and finally (3) sizing and dispatch optimization. The fully-decoupled design achieves a cycle efficiency of 43.1%, an enhancement over the vendor’s standard efficiency of 42.2% (Xe-100 design). Here, the proposed design offers strengthened physical barriers from the nuclear island as well as superior operational flexibility and power boosting. Dispatch optimization and market analysis reveal that thermal energy storage size is highly dependent on the peak patterns of electricity prices and the minimum generation level constraint imposed on the balance of plant. Evaluation of off-design operation demonstrates that the full decoupling design with the suggested fail-safe control mechanisms ensures a minimal impact on reactor parameters, even during rapid power ramping.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Thermal coupling-decoupling mechanism of heat transfer across van der Waals interfaces in n-eicosane

Progress toward improving thermal transport properties of n-eicosane, a promising phase change material for thermal energy storage near human body temperature, is hindered by lack of a general theoretical framework to model thermal interfacial conductance (TIC) of the van der Waals (vdW) force bonded molecular interfaces, which have little compositional/structural mismatch. Combining molecular dynamics simulations at temperatures up to the melting point and a time-domain analysis of interfacial heat currents in individual molecules, we unveil that (1) the heat flux across a molecular vdW interface has an alternating coupling-decoupling pattern at the single molecule level due to thermal fluctuations, and (2) the net heat transfer during the thermally coupled periods is orders of magnitude larger than that during the thermally decoupled periods. Furthermore, we demonstrate that a vdW interface's TIC correlates almost linearly with two atomistic-scale coupling-decoupling parameters: αc and σc, that represent the duration and strength of the thermal coupling, respectively. This thermal coupling-decoupling mechanism proposes a new paradigm that explicitly accounts for the effects of structural flexibility and dynamical fluctuation on heat transfer across molecular interfaces, and will likely provide new insights into modeling thermal transport properties in a wide-ranging soft materials, including self-assembled monolayers, paraffins or lipids.

42 ENGINEERING↗

Ecohydrological decoupling under changing disturbances and climate

Terrestrial disturbances are increasing in frequency and severity, perturbing the hydrologic cycle by altering vegetation-mediated water use and microclimate. Changes in the hydrological cycle alter vegetation succession, which is additionally influenced by changing climate and atmospheric CO 2 . Here, the interacting drivers and feedbacks between disturbances, climate, and vegetation cause uncertainty regarding the sustainable provision of freshwater through streamflow. Here we synthesize the literature on post-disturbance ecohydrological coupling, in particular, including the mechanistic relationship between vegetation and streamflow, under changing disturbance regimes, atmospheric CO 2 , and climate. Disturbance can cause decoupling between transpiration and streamflow by altering the connectivity, size, availability, and spatial distribution of their source pools. Decoupling increases when soil moisture is low due to reduced connectivity, and when soil moisture is high and Q and T are independent. Successional trajectories regulate the physiological and physical features influencing influence the dynamics of source water partitioning. Changing climate and disturbance regimes can alter succession and prolong decoupling, with potential moderation by CO 2 . Increasing rates, severity, and spread of disturbances along with warming could promote greater decoupling globally. From this review emerges a framework of testable hypotheses that identify the critical processes regulating ecohydrological coupling and provides a roadmap for future research. Accurate prediction of post-disturbance coupling and subsequent water availability for human consumption requires understanding the degree of hydraulic connectivity between source water pools for transpiration and streamflow and their response to succession under changing disturbance and climate regimes.

54 ENVIRONMENTAL SCIENCES↗

Effect of Chain Rigidity on the Decoupling of Ion Motion from Segmental Relaxation in Polymerized Ionic Liquids: Ambient and Elevated Pressure Studies

Conductivity in polymer electrolytes has been generally discussed with the assumption that the segmental motions control charge transport. However, much less attention has been paid to the mechanism of ion conductivity where the motions of ions are less dependent (decoupled) on segmental dynamics. We present that this phenomenon is observed in ionic materials as they approach their glass transition temperature and becomes essential for design and development of highly conducting solid polymer electrolytes. In this paper, we study the effect of chain rigidity on the decoupling of ion transport from segmental motion in three polymerized ionic liquids (polyILs) containing the same cation–anion pair but differing in flexibility of the polymer backbones and side groups. Analysis of dielectric and rheology data reveals that decoupling is strong in vinyl-based rigid polymers while almost negligible in novel siloxane-based flexible polyILs. To explain this behavior, we investigated ion and chain dynamics at ambient and elevated pressure. Our results suggest that decoupling has a direct relationship to the frustration in chain packing and free volume. Finally, these conclusions are also supported by coarse-grained molecular dynamics simulations.

36 MATERIALS SCIENCE↗