Hysteresis is observed in sorption-induced swelling in various soft nanoporous polymers. The associated coupling mechanism responsible for the observed sorption-induced swelling and associated ...hysteresis needs to be unraveled. Here we report a microscopic scenario for the molecular mechanism responsible for hysteresis in sorption-induced swelling in natural polymers such as cellulose using atom-scale simulation; moisture content and swelling exhibit hysteresis upon ad- and desorption but not swelling versus moisture content. Different hydrogen bond networks are examined; cellulose swells to form water-cellulose bonds upon adsorption but these bonds do not break upon desorption at the same chemical potential. These findings, which are supported by mechanical testing and cellulose textural assessment upon sorption, shed light on experimental observations for wood and other related materials.
Droplet impact has been imaged on different rigid, smooth, and rough substrates for three liquids with different viscosity and surface tension, with special attention to the lower impact velocity ...range. Of all studied parameters, only surface tension and viscosity, thus the liquid properties, clearly play a role in terms of the attained maximum spreading ratio of the impacting droplet. Surface roughness and type of surface (steel, aluminum, and parafilm) slightly affect the dynamic wettability and maximum spreading at low impact velocity. The dynamic contact angle at maximum spreading has been identified to properly characterize this dynamic spreading process, especially at low impact velocity where dynamic wetting plays an important role. The dynamic contact angle is found to be generally higher than the equilibrium contact angle, showing that statically wetting surfaces can become less wetting or even nonwetting under dynamic droplet impact. An improved energy balance model for maximum spreading ratio is proposed based on a correct analytical modeling of the time at maximum spreading, which determines the viscous dissipation. Experiments show that the time at maximum spreading decreases with impact velocity depending on the surface tension of the liquid, and a scaling with maximum spreading diameter and surface tension is proposed. A second improvement is based on the use of the dynamic contact angle at maximum spreading, instead of quasi-static contact angles, to describe the dynamic wetting process at low impact velocity. This improved model showed good agreement compared to experiments for the maximum spreading ratio versus impact velocity for different liquids, and a better prediction compared to other models in literature. In particular, scaling according to We1/2 is found invalid for low velocities, since the curves bend over to higher maximum spreading ratios due to the dynamic wetting process.
In this work, a numerical model for isothermal liquid–vapor phase change (evaporation) of the two-component air–water system is proposed based on the pseudopotential lattice Boltzmann method. Through ...the Chapman–Enskog multiscale analysis, we show that the model can correctly recover the macroscopic governing equations of the multicomponent multiphase system with a built-in binary diffusion mechanism. The model is verified based on the two-component Stefan problem where the measured binary diffusivity is consistent with theoretical analysis. The model is then applied to convective drying of a dual-porosity porous medium at the pore scale. The simulation captures a classical transition in the drying process of porous media, from the constant rate period (CRP, first phase) showing significant capillary pumping from large to small pores, to the falling rate period (FRP, second phase) with the liquid front receding in small pores. It is found that, in the CRP, the evaporation rate increases with the inflow Reynolds number (Re), while in the FRP, the evaporation curves almost collapse at different Res. The underlying mechanism is elucidated by introducing an effective Péclet number (Pe). It is shown that convection is dominant in the CRP and diffusion in the FRP, as evidenced by Pe > 1 and Pe < 1, respectively. We also find a log-law dependence of the average evaporation rate on the inflow Re in the CRP regime. The present work provides new insights into the drying physics of porous media and its direct modeling at the pore scale.
•Coupling mechanism of sorption and deformation is reviewed by molecular simulations.•Poromechanics model is developed based on the coupling mechanism at nanoscale.•Different types of sorption ...isotherms exhibited by different adsorbent-adsorbate systems are quantitatively explained by the developed model.•Influences of material properties on the coupled behavior of sorption and deformation are characterized.
The coupling of water sorption and deformation in soft nanoporous polymers is studied by means of statistical mechanics molecular simulation and the general framework of poromechanics. It is shown that the large amount of water adsorbed by soft nanoporous polymers under free swelling condition results from sorption-induced deformation, which generates more inter-chain space to accommodate water molecules. A poromechanical model is proposed to describe this coupled behavior from the molecular simulation data without any arbitrary fitting. More in detail, by taking into account the mechanical properties, sorption characteristics and structural information as a function of water loading, the model agrees with the molecular simulation and accurately captures the coupling mechanism. Using this model, it is also shown that distinct sorption and deformation behaviors can be observed depending on the material properties. On the one hand, small mechanical modulus, strong adsorbent-adsorbate interaction and significant coupling between sorption/deformation lead to Type II sorption isotherms (with larger sorption amount and sorption-induced deformation). On the other hand, Type I sorption isotherms with limited sorption amount and sorption-induced deformation are obtained for materials with opposite properties.
Droplet wetting and distortion on flat surfaces with heterogeneous wettability are studied using the 3D Shan–Chen pseudopotential multiphase lattice Boltzmann model (LBM). The contact angles are ...compared with the Cassie mode, which predicts an apparent contact angle for flat surfaces with different wetting properties, where the droplet size is large compared to the size of the heterogeneity. In this study, the surface studied consists in a regular checkboard pattern with two different Young’s contact angles (hydrophilic and hydrophobic) and equal surface fraction. The droplet size and patch size of the checkboard are varied beyond the limit where Cassie’s equation is valid. A critical ratio of patch size to droplet radius is found below which the apparent contact angle follows the Cassie mode. Above the critical value, the droplet shape changes from a spherical cap to a more distorted form, and no single contact angle can be determined. The local contact angles are found to vary along the contact line between minimum and maximum values. The droplet is found to wet preferentially the hydrophilic region, and the wetted area fraction of the hydrophilic region increases quasi-linearly with the ratio between patch and droplet sizes. We propose a new equation beyond the critical ratio, defining an equivalent contact angle, where the wetted area fractions are used as weighting coefficients for the maximum and minimum local contact angles. This equivalent contact angle is found to equal Cassie’s contact angle.
The quintessential form of cellulose in wood consists of microfibrils that have high aspect ratio crystalline domains embedded within an amorphous cellulose domain. In this study, we apply ...united-atom molecular dynamics simulations to quantify changes in different morphologies of cellulose. We compare the structure of crystalline cellulose with paracrystalline and amorphous phases that are both obtained by high temperature equilibration followed by quenching at room temperature. Our study reveals that the paracrystalline phase may be an intermediate, kinetically arrested phase formed upon amorphisation of crystalline cellulose. The quenched structures yield isotropic amorphous polymer domains consistent with experimental results, thereby validating a new computational protocol for achieving amorphous cellulose structure. The non-crystalline cellulose compared to crystalline structure is characterized by a dramatic decrease in elastic modulus, thermal expansion coefficient, bond energies, and number of hydrogen bonds. Analysis of the lattice parameters shows that Iβ cellulose undergoes a phase transition into high-temperature phase in the range of 450–550 K. The mechanisms of the phase transition elucidated here present an atomistic view of the temperature dependent dynamic structure and mechanical properties of cellulose. The paracrystalline state of cellulose exhibits intermediate mechanical properties, between crystalline and amorphous phases, that can be assigned to the physical properties of the interphase regions between crystalline and amorphous cellulose in wood microfibrils. Our results suggest an atomistic structural view of amorphous cellulose which is consistent with experimental data available up to date and provide a basis for future multi-scale models for wood microfibrils and all-cellulose nanocomposites.
Drying of porous media is governed by a combination of evaporation and movement of the liquid phase within the porous structure. Contact angle hysteresis induced by surface roughness is shown to ...influence multi-phase flows, such as contact line motion of droplet, phase distribution during drainage and coffee ring formed after droplet drying in constant contact radius mode. However, the influence of contact angle hysteresis on liquid drying in porous media is still an unanswered question. Lattice Boltzmann model (LBM) is an advanced numerical approach increasingly used to study phase change problems including drying. In this paper, based on a geometric formulation scheme to prescribe contact angle, we implement a contact angle hysteresis model within the framework of a two-phase pseudopotential LBM. The capability and accuracy of prescribing and automatically measuring contact angles over a large range are tested and validated by simulating droplets sitting on flat and curved surfaces. Afterward, the proposed contact angle hysteresis model is validated by modeling droplet drying on flat and curved surfaces. Then, drying of two connected capillary tubes is studied, considering the influence of different contact angle hysteresis ranges on drying dynamics. Finally, the model is applied to study drying of a dual-porosity porous medium, where phase distribution and drying rate are compared with and without contact angle hysteresis. The proposed model is shown to be capable of dealing with different contact angle hysteresis ranges accurately and of capturing the physical mechanisms during drying in different porous media including flat and curved geometries.
Abstract We introduce a novel methodological advancement by clustering paired near-surface air temperature with the planetary boundary layer height to characterize intra-city clusters for analytics. ...To illustrate this approach, we analyze three heatwaves (HWs): the 2019 HW in Paris, the 2018 HW in Montreal, and the 2017 HW in Zurich. We assess cluster-based characteristics before, during, and after heatwave events. While the urban clusters identified by this clustering align well with built-up areas obtained from the Moderate Resolution Imaging Spectroradiometer (MODIS) land cover data, additional local hot spots spanning several kilometers can also be recognized, extending outside the built-up areas. Using the objective hysteresis model, we further determine the overall strength coefficient of the hysteresis loop between ground storage flux and all-wave downward radiative flux, ranging from 0.414 to 0.457 for urban clusters and from 0.126 to 0.157 for rural clusters during the heatwave periods. Across all cities, we observe a consistent refueling-restoration mode in the cumulative ground heat flux as the heatwaves progress. Future developments of this proposed two-component clustering approach, with the integration of more influential physics and advances in spatial and temporal resolutions, will offer a more comprehensive characterization of cities for urban climate analytics.
As cities and their population are subjected to climate change and urban heat islands, it is paramount to have the means to understand the local urban climate and propose mitigation measures, ...especially at neighbourhood, local and building scales. A framework is presented, where the urban climate is studied by coupling a meteorological model to a building-resolved local urban climate model, and where an urban climate model is coupled to a building energy simulation model. The urban climate model allows for studies at local scale, combining modelling of wind and buoyancy with computational fluid dynamics, radiative exchange and heat and mass transport in porous materials including evaporative cooling at street canyon and neighbourhood scale. This coupled model takes into account the hygrothermal behaviour of porous materials and vegetation subjected to variations of wetting, sun, wind, humidity and temperature. The model is driven by climate predictions from a mesoscale meteorological model including urban parametrisation. Building energy demand, such as cooling demand during heat waves, can be evaluated. This integrated approach not only allows for the design of adapted buildings, but also urban environments that can mitigate the negative effects of future climate change and increased urban heat islands. Mitigation solutions for urban heat island effect and heat waves, including vegetation, evaporative cooling pavements and neighbourhood morphology, are assessed in terms of pedestrian comfort and building (cooling) energy consumption.
Wood and wood materials are highly sensitive to moisture in the environment. To a large extent this relates to the hygroscopicity of wood hemicelluloses. In order to increase our understanding of the ...effects of moisture sorption of the major wood hemicelluloses, glucomannan and xylan, model experiments using films of amorphous konjak glucomannan and rye arabinoxylan were conducted. Moisture-induced expansion and stiffness softening were characterized using dynamic mechanical testing. Both hemicelluloses showed a threshold around 5 % of moisture content above which swelling increased whereas the modulus decreased by more than 70 %. FTIR spectra, using H
2
O and D
2
O, indicated that even at high RH about 15 % of the hydroxyl groups were not accessible to hydrogen exchange by D
2
O. For xylan both hydroxyl groups were found to exchange in the same manner while for the glucomannan the O(6)H group seemed to be the most accessible.
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