Physical Origins of Thermal Properties of Cement Paste

Despite the ever-increasing interest in multiscale porous materials, the chemophysical origin of their thermal properties at the nanoscale and its connection to the macroscale properties still remain rather obscure. In this paper, we link the atomic- and macroscopic-level thermal properties by combining tools of statistical physics and mean-field homogenization theory. We begin with analyzing the vibrational density of states of several calcium-silicate materials in the cement paste. Unlike crystalline phases, we indicate that calcium silicate hydrates (CSH) exhibit extra vibrational states at low frequencies (<2  THz) compared to the vibrational states predicted by the Debye model. This anomaly is commonly referred to as the boson peak in glass physics. In addition, the specific-heat capacity of CSH in both dry and saturated states scales linearly with the calcium-to-silicon ratio. We show that the nanoscale-confining environment of CSH decreases the apparent heat capacity of water by a factor of 4. Furthermore, full thermal conductivity tensors for all phases are calculated via the Green-Kubo formalism. We estimate the mean free path of phonons in calcium silicates to be on the order of interatomic bonds. This satisfies the scale separability condition and justifies the use of mean-field homogenization theories for upscaling purposes. Upscaling schemes yield a good estimate of the macroscopic specific-heat capacity and thermal conductivity of cement paste during the hydration process, independent of fitting parameters.Portland Cement AssociationNational Ready Mixed Concrete Association (Research and Education Foundation

Bottom-up model of adsorption and transport in multiscale porous media

We develop a model of transport in multiscale porous media which accounts for adsorption in the different porosity scales. This model employs statistical mechanics to upscale molecular simulation and describe adsorption and transport at larger time and length scales. Using atom-scale simulations, which capture the changes in adsorption and transport with temperature, pressure, pore size, etc., this approach does not assume any adsorption or flow type. Moreover, by relating the local chemical potential μ(r) and density ρ(r), the present model accounts for adsorption effects and possible changes in the confined fluid state upon transport. This model constitutes a bottom-up framework of adsorption and transport in multiscale materials as it (1) describes the adsorption-transport interplay, (2) accounts for the hydrodynamics breakdown at the nm scale, and (3) is multiscale.France. Investissements d'avenir (ICoME2/ANR-11-LABX-0053)France. Investissements d'avenir (A*NUDEX/ANR-11-IDEX-0001-02)Schlumberger FoundationShell Oil Compan

Comparison of potato varieties between seasons and their potential for acrylamide formation

BACKGROUND: Acrylamide is a probable human carcinogen produced during food preparation, including frying of potato products. The aim of this study was to investigate the impact of seasonal variation on tuber composition and its acrylamide generation potential. RESULTS: The chemical composition of potato varieties used respectively for French fry (Bintje and Ramos) and crisp (Lady Rosetta and Saturna) production was studied throughout a storage period of 9 months during two growing seasons (2003 and 2004), in addition to their acrylamide generation potential during preparation of French fries. A significant impact of variable climatological conditions on the reducing sugar, dry matter, total free amino acid and free asparagine contents of tubers was observed. Exceptionally warm summers gave rise to a lower reducing sugar content (expressed on a dry matter basis) and thus a lower susceptibility to acrylamide generation during frying. CONCLUSION: It cannot be excluded that potato growers and the potato-processing industry are confronted with some harvests that are more prone to acrylamide generation than others owing to climatological variability, thus confirming the importance of a multifactorial approach to mitigate acrylamide generation in potato products.</p

Mesoscale Poroelasticity of Heterogeneous Media

The poromechanics of heterogeneous media is reformulated in a discrete framework using the lattice element method (LEM) that accounts for the presence of interfaces as well as local microtextural and elastic variations. The exchange of mechanical information between pore and solid(s) is captured by means of force field potentials for these domains, which eliminate the requirement of scale separability of continuum-based poromechanics approaches. In congruence with μVT and NPT ensembles of statistical mechanics, discrete expressions for Biot poroelastic coefficients are derived. Considering harmonic-type interaction potentials for each link, analytical expressions for both isotropic and transversely isotropic effective elasticity are presented. The theory is validated against continuum-based expressions of Biot poroelastic coefficients for porous media with isotropic and transversely isotropic elastic solid behavior

Subcontinuum mass transport of condensed hydrocarbons in nanoporous media

Although hydrocarbon production from unconventional reservoirs, the so-called shale gas, has exploded recently, reliable predictions of resource availability and extraction are missing because conventional tools fail to account for their ultra-low permeability and complexity. Here, we use molecular simulation and statistical mechanics to show that continuum description—Darcy’s law—fails to predict transport in shales nanoporous matrix (kerogen). The non-Darcy behaviour arises from strong adsorption in kerogen and the breakdown of hydrodynamics at the nanoscale, which contradict the assumption of viscous flow. Despite this complexity, all permeances collapse on a master curve with an unexpected dependence on alkane length. We rationalize this non-hydrodynamic behaviour using a molecular description capturing the scaling of permeance with alkane length and density. These results, which stress the need for a change of paradigm from classical descriptions to nanofluidic transport, have implications for shale gas but more generally for transport in nanoporous media.France. Investissements d'avenir (ICoME2 Labex ANR-11-LABX-0053)France. Investissements d'avenir (A*MIDEX ANR-11-IDEX-0001-02)Royal Dutch-Shell GroupSchlumberger Foundatio

Rigidity Transition in Materials: Hardness is Driven by Weak Atomic Constraints

Understanding the composition dependence of the hardness in materials is of primary importance for infrastructures and handled devices. Stimulated by the need for stronger protective screens, topological constraint theory has recently been used to predict the hardness in glasses. Herein, we report that the concept of rigidity transition can be extended to a broader range of materials than just glass. We show that hardness depends linearly on the number of angular constraints, which, compared to radial interactions, constitute the weaker ones acting between the atoms. This leads to a predictive model for hardness, generally applicable to any crystalline or glassy material

Effect of financial incentives on incentivised and non-incentivised clinical activities: longitudinal analysis of data from the UK Quality and Outcomes Framework

This is the final version. Available on open access from BMJ Publishing Group via the DOI in this recordData sharing: Technical appendix and statistical code available from the corresponding author ([email protected]). The dataset was derived from the General Practice Research Database and is not available from the authors, but it can be derived on application to GPRD.OBJECTIVE: To investigate whether the incentive scheme for UK general practitioners led them to neglect activities not included in the scheme. DESIGN: Longitudinal analysis of achievement rates for 42 activities (23 included in incentive scheme, 19 not included) selected from 428 identified indicators of quality of care. SETTING: 148 general practices in England (653 500 patients). MAIN OUTCOME MEASURES: Achievement rates projected from trends in the pre-incentive period (2000-1 to 2002-3) and actual rates in the first three years of the scheme (2004-5 to 2006-7). RESULTS: Achievement rates improved for most indicators in the pre-incentive period. There were significant increases in the rate of improvement in the first year of the incentive scheme (2004-5) for 22 of the 23 incentivised indicators. Achievement for these indicators reached a plateau after 2004-5, but quality of care in 2006-7 remained higher than that predicted by pre-incentive trends for 14 incentivised indicators. There was no overall effect on the rate of improvement for non-incentivised indicators in the first year of the scheme, but by 2006-7 achievement rates were significantly below those predicted by pre-incentive trends. CONCLUSIONS: There were substantial improvements in quality for all indicators between 2001 and 2007. Improvements associated with financial incentives seem to have been achieved at the expense of small detrimental effects on aspects of care that were not incentivised.There was no direct funding for this study, but the National Primary Care Research and Development Centre receives core funding from the UK Department of Health

Thermodynamics, kinetics, and mechanics of cesium sorption in cement paste: A multiscale assessment

Cesium-137 is a common radioactive byproduct found in nuclear spent fuel. Given its 30 year half life, its interactions with potential storage materials—such as cement paste—is of crucial importance. In this paper, simulations are used to establish the interaction of calcium silicate hydrates (C-S-H)—the main binding phase of cement paste—with Cs at the nano- and mesoscale. Different C-S-H compositions are explored, including a range of Ca/Si ratios from 1.0 to 2.0. These calculations are based on a set of 150 atomistic models, which qualitatively and quantitatively reproduce a number of experimentally measured features of C-S-H—within limits intrinsic to the approximations imposed by classical molecular dynamics and the steps followed when building the models. A procedure where hydrated Ca[superscript 2+] ions are swapped for Cs[superscript 1+] ions shows that Cs adsorption in the C-S-H interlayer is preferred to Cs adsorption at the nanopore surface when Cs concentrations are lower than 0.19 Mol/kg. Interlayer sorption decreases as the Ca/Si ratio increases. The activation relaxation technique nouveau is used to access timescales out of the reach of traditional molecular dynamics (MD). It indicates that characteristic diffusion time for Cs[superscript 1+] in the C-S-H interlayer is on the order of a few hours. Cs uptake in the interlayer has little impact on the elastic response of C-S-H. It leads to swelling of the C-S-H grains, but mesoscale calculations that access length scales out of the range of MD indicate that this leads to practically negligible expansive pressures for Cs concentrations relevant to nuclear waste repositories

Quality of care assessment for people with multimorbidity.

Multimorbidity, the simultaneous presence of multiple health conditions in an individual, is an increasingly common phenomenon globally. The systematic assessment of the quality of care delivered to people with multimorbidity will be key to informing the organization of services for meeting their complex needs. Yet, current assessments tend to focus on single conditions and do not capture the complex processes that are required for providing care for people with multimorbidity. We conducted a scoping review on quality of care and multimorbidity in selected databases in June 2018 and identified 87 documents as eligible for review, predominantly original research and reviews from North America, Europe and Australasia and mostly frequently related to primary care settings. We synthesized data qualitatively in terms of perceived challenges, evidence and proposed metrics. Findings reveal that the association between quality of care and multimorbidity is complex and depends on the conditions involved (quality appears to be higher for those with concordant conditions, and lower in the presence of discordant conditions) and the approach used for measuring quality (quality appears to be higher in people with multimorbidity when measured using condition/drug-specific process or intermediate outcome indicators, and worse when using patient-centred reports of experiences of care). People with discordant multimorbidity may be disadvantaged by current approaches to quality assessment, particularly when they are linked to financial incentives. A better understanding of models of care that best meet the needs of this group is needed for developing appropriate quality assessment frameworks. Capturing patient preferences and values and incorporate patients' voices in the form of patient-reported experiences and outcomes of care will be critical towards the achievement of high-performing health systems that are responsive to the needs of people with multimorbidity

Topological Control on the Structural Relaxation of Atomic Networks under Stress

Upon loading, atomic networks can feature delayed irreversible relaxation. However, the effect of composition and structure on relaxation remains poorly understood. Herein, relying on accelerated molecular dynamics simulations and topological constraint theory, we investigate the relationship between atomic topology and stress-induced structural relaxation, by taking the example of creep deformations in calcium silicate hydrates (C─S─H), the binding phase of concrete. Under constant shear stress, C─S─H is found to feature delayed logarithmic shear deformations. We demonstrate that the propensity for relaxation is minimum for isostatic atomic networks, which are characterized by the simultaneous absence of floppy internal modes of relaxation and eigenstress. This suggests that topological nanoengineering could lead to the discovery of nonaging materials.National Science Foundation (U.S.) (Grant 1562066)Schlumberger-Doll Research CenterMassachusetts Institute of Technology. Concrete Sustainability HubMassachusetts Institute of Technology. Interdisciplinary Center on MultiScale Material Science for Energy and Environment (Grant ANR-11-LABX-0053)Massachusetts Institute of Technology. Interdisciplinary Center on MultiScale Material Science for Energy and Environment (Grant ANR-11-IDEX-0001- 02