Soft Porous Materials Research Articles

Ethylene control in fruit quality assurance: A material science perspective

AbstractThe waste of resources associated with fruit decay is rapidly spreading globally, threatening the interests of relevant practitioners and the health of consumer groups, and demanding precise solutions. Controlling fruit ripening through ethylene regulation is one of the most important strategies for providing high‐quality fruits. However, current materials for ethylene regulation still have difficulty realizing their application potential due to high manufacturing costs and performance deficiencies. In this review, the ethylene‐controlled release materials for ripening based on molecular encapsulation and the ethylene scavengers for preservation based on mechanisms such as oxidation, photodegradation, and adsorption are presented. We discuss and analyze a wide range of materials in terms of mechanism, performance, potential of applicability, and sustainability. The ethylene release behavior of encapsulating materials depends on the form in which the ethylene binds to the material as well as on environmental factors (humidity and temperature). For ethylene scavengers, there are a variety of scavenging mechanisms, but they generally require porous materials as adsorption carriers. We highlight the great opportunity of designing soft crystalline porous materials as efficient ethylene adsorbent due to their unique structural properties. We present this review, including a summary of practical characteristics and deficiencies of various materials, to establish a systematic understanding of fruit quality assurance materials applied to ethylene regulation, anticipating a promising prospect for these new materials.

A large deformation multiphase continuum mechanics model for shock loading of soft porous materials

AbstractA large deformation, coupled finite‐element (FE) model is developed to simulate the multiphase response of soft porous materials subjected to high strain‐rate loading. The approach is based on the theory of porous media (TPM) at large deformations. Simplifications to the one‐dimensional regime studied in the numerical simulations follow. An overview of several different time integration schemes is presented for the purpose of solving the nonlinear dynamic coupled balance of momenta (mixture and fluid) and balance of mass of the mixture equations. Numerical examples are presented for (i) verification against closed‐form analytical solutions assuming small loads, (ii) demonstrating large deformation effects at high strain‐rate, and (iii) showing differences in deformations between a single‐phase elastodynamics model with occluded compressible pore fluid and a multiphase poroelastodynamics model at high strain‐rate. The multiphase model shows that the relative motion of the pore fluid significantly dampens the deformation response of the solid skeleton as compared to the single‐phase model, and makes it possible to extract quantitative values for the stresses of the different constituents, thereby allowing one to form preliminary conclusions about the onset of damage in the solid skeleton. The novelty of the current work is developing a multiphase, large deformation, mixture theory numerical model for high strain‐rate loading of soft porous materials. It was discovered that explicit, adaptive time‐stepping Runge–Kutta schemes offer high accuracy at relatively low cost when compared to traditional implicit or explicit central difference time‐stepping schemes for shock‐like loadings. Shock viscosity is added to the mixture momentum balance equation to regularize the shock front, and a stabilization term is added to the mixture mass balance equation to stabilize equal order interpolation finite elements for the coupled finite element solution of multiphase materials.

Flow and deformation due to periodic loading in a soft porous material

Soft porous materials, such as biological tissues and soils, are exposed to periodic deformations in a variety of natural and industrial contexts. The detailed flow and mechanics of these deformations have not yet been systematically investigated. Here, we fill this gap by identifying and exploring the complete parameter space associated with periodic deformations in the context of a one-dimensional model problem. We use large-deformation poroelasticity to consider a wide range of loading periods and amplitudes. We identify two distinct mechanical regimes, distinguished by whether the loading period is slow or fast relative to the characteristic poroelastic timescale. We develop analytical solutions for slow loading at any amplitude and for infinitesimal amplitude at any period. We use these analytical solutions and a full numerical solution to explore the localisation of the deformation near the permeable boundary as the period decreases and the emergence of nonlinear effects as the amplitude increases. We show that large deformations lead to asymmetry between the loading and unloading phases of each cycle in terms of the distributions of porosity and fluid flux.

Pressure effects on the resonant attenuation of soft porous beads-based materials for underwater acoustics

Dedicated coating materials for anechoism and furtivity in underwater acoustics must exhibit a strong reliability regarding their mechanical resistance to hydrostatic pressure. Soft porous materials, especially, a distribution of soft porous beads within a polyurethane matrix, have been previously proposed as an acoustic insulator device. The purpose of the present letter is to investigate the attenuation efficiency of soft porous silicone beads-based materials while being exposed to uniaxial loads mimicking hydrostatic pressures encountered in underwater acoustics. The acoustic performance of this locally resonant material is then compared to the classical coating technology using micro-balloons. The use of an adapted surfactant (a silicone alkyl polyether compound) in the fabrication process of the soft porous silicone-based beads, obtained through an emulsion templating process, leads to particles exhibiting an open porosity. The (resonant) attenuation of the soft porous beads-based material remains greater than the micro-balloons-based material until several bars. Above this critical resilience value, the mechanical stress irreversibly damages the soft porous beads.

Surface Assessment via Grid Evaluation (SuAVE) for Every Surface Curvature and Cavity Shape.

The surface assessment via grid evaluation (SuAVE) software was developed to account for the effect of curvature in the calculations of structural properties of chemical interfaces regardless of the chemical composition, asymmetry, and level of atom coarseness. It employs differential geometry techniques, enabling the representation of chemical surfaces as fully differentiable. In this article, we present novel developments of SuAVE to treat closed surfaces and complex cavity shapes. These developments expand the repertoire of curvature-dependent analyses already available in the previous version of SuAVE (e.g., area per lipid, density profiles, membrane thickness, deuterium-order parameters, volume per lipid, and surface curvature angle) to include new functionalities applicable to soft matter (e.g., sphericity, average radius, principal moment of inertia, and roundness) and crystalline porous materials (e.g., pore diameter, internal void volume, total area, and the total void volume of the unit cell structure). SuAVE can accurately handle chemical systems with high and low atom density as demonstrated for two distinct chemical systems: the lipid A vesicle and a set of selected metal–organic frameworks. The SuAVE software v2.0 is fully parallel and benefits from a compiler that supports OpenMP. SuAVE is freely available from https://github.com/SuAVE-Software/source and https://www.biomatsite.net/.

Dynamic network of intermolecular interactions in metal-organic frameworks functionalized by molecular machines.

Molecular machines enable external control of structural and dynamic phenomena at the atomic level. To efficiently transfer their tunable properties into designated functionalities, a detailed understanding of the impact of molecular embedding is needed. In particular, a comprehensive insight is fundamental to design hierarchical multifunctional systems that are inspired by biological cells. Here, we applied an on-the-fly trained force field to perform atomistic simulations of a systematically modified rotaxane functionalized metal-organic framework. Our atomistic studies reveal a symmetric and asymmetric interplay of the mechanically bonded rings (MBRs) within the framework depending on the local environment. As a result, their translational motion is modulated ranging from fast oscillatory behavior to cooperative and potentially directed shuttling. The derived picture of competitive interactions, which influence the operation mechanism of the MBRs embedded in these soft porous materials, promotes the development of responsive functional materials, which is a key step toward intelligent matter.

Fluid–fluid phase separation in a soft porous medium

Various biological and chemical processes lead to the nucleation and growth of non-wetting fluid bubbles within the pore space of a granular medium, such as the formation of gas bubbles in liquid-saturated lake-bed sediments. In sufficiently soft porous materials, the non-wetting nature of these bubbles can result in the formation of open cavities within the granular solid skeleton. Here, we consider this process through the lens of phase separation, where thermomechanics govern the separation of the non-wetting phase from a fluid–fluid–solid mixture. We construct a phase-field model informed by large-deformation poromechanics, in which two immiscible fluids interact with a poroelastic solid skeleton. Our model captures the competing effects of elasticity and fluid–fluid–solid interactions. We use a phase-field damage model to capture the mechanics of the granular solid. As a model problem, we consider an initial distribution of non-wetting fluid in the pore space that separates into multiple cavities. We use simulations and linear-stability analysis to identify the key parameters that control phase separation, the conditions that favour the formation of cavities, and the characteristic size of the resulting cavities.

Deformation Localization and Damage Constitutive Model of Raw Coal and Briquette Coal under Uniaxial Compression

In order to compare and analyze the difference in deformation and damage law of soft and hard porous media materials, the digital image correlation is used to evaluate the heterogeneous development of strain fields of hard and brittle raw coal material and soft plastic briquette coal material under uniaxial compression. Through the defined statistical indicator, the quantitative characterization of deformation localization is realized, and the material damage constitutive model based on the statistical indicator of strain field is established. The results show that the yield stage of raw coal is not obvious, showing the characteristics of strain hardening and X-shaped macroscopic shear failure. The yield stage of briquette coal is more obvious, showing the characteristics of strain softening and a tensile failure mode. The progress of strain localization can well reflect the damage and destruction process of materials. The progress of strain localization of briquette coal can be divided into uniform deformation stage, localization stage, and failure stage, while the stage characteristics of localized evolution of raw coal is not obvious. The theoretical results of the damage constitutive model defined by statistical indicator are in good agreement with the experimental data and can well reflect the stress and strain characteristics of the two materials.

Impact properties of uniaxially thermoformed auxetic foams

This work describes large strain quasi-static and impact tests of a new class of low-cost, uniaxially thermoformed, transverse isotropic auxetic foams with compression ratio ranging from 20 to 80%. A custom drop tower rig with high-speed cameras suitable for these soft porous foam materials is designed and used to perform impact tests with energy ranging from 0.38 to 1.90 J, corresponding to strain rates from 64/s to 143/s. The thermoformed foams only show auxeticity when loaded along the transverse direction to the uniaxial thermoforming compression, with Poisson's ratio V21 reaching as low as −1.5 at 20% strain and then close to 0 at large strains. The samples deform with large shear band deformations, also due to the auxeticity. The negative Poisson's ratio foams along that transverse direction also show enhanced impact energy absorption performance, with normalized peak force reduction as high as ∼40% against the pristine foam; the reduction is however 20% along the thermoforming direction. A constitutive model based on Nagy's approach is applied to describe the enhancement of dynamic stress during the impact tests compared with the quasi-static one, due to strain rate effects.

Fluids Alter Elasticity Measurements: Porous Wave Propagation Accounts for Shear Wave Dispersion in Elastography

In shear wave elastography, rotational wave speeds are converted to elasticity measures using elastodynamic theory. The method has a wide range of applications and is the gold standard for non-invasive liver fibrosis detection. However, the observed shear wave dispersion of in vivo human liver shows a mismatch with purely elastic and visco-elastic wave propagation theory. In a laboratory phantom experiment we demonstrate that porosity and fluid viscosity need to be considered to properly convert shear wave speeds to elasticity in soft porous materials. We extend this conclusion to the clinical application of liver stiffness characterization by revisiting in vivo studies of liver elastography. To that end we compare Biot’s theory of poro-visco-elastic wave propagation to Voigt’s visco-elastic model. Our results suggest that accounting for dispersion due to fluid viscosity could improve shear wave imaging in the liver and other highly vascularized organs.

Translocation Dynamics of High-Internal Phase Double Emulsions in Narrow Channels.

We numerically study the translocation dynamics of double emulsion drops with multiple close-packed inner droplets within constrictions. Such liquid architectures, which we refer to as HIPdEs (high-internal phase double emulsions), consist of a ternary fluid, in which monodisperse droplets are encapsulated within a larger drop in turn immersed in a bulk fluid. Extensive two-dimensional lattice Boltzmann simulations show that if the area fraction of the internal drops is close to the packing fraction limit of hard spheres and the height of the channel is much smaller than the typical size of the emulsion, the crossing yields permanent shape deformations persistent over long periods of time. Morphological changes and rheological response are quantitatively assessed in terms of the structure of the velocity field, circularity of the emulsion, and rate of energy dissipated by viscous forces. Our results may be used to improve the design of soft mesoscale porous materials, which employ HIPdEs as templates for tissue engineering applications.

Modeling the extended reaction of porous absorbers in time-domain wave-based room acoustic simulations

The absorption properties of room surfaces have a major influence on the acoustics of rooms. In wave-based room acoustic simulations it is common practice to model room surfaces using a local-reaction approximation, instead of modeling the full extended-reaction behavior. However, previous research has indicated that the local-reaction assumption is not appropriate for surfaces that have elastic properties or fluid layers, such as soft porous materials, porous materials backed by an air cavity and airtight membranes. In this talk we present a method for incorporating the extended-reaction behavior of porous absorbers into a time-domain discontinuous Galerkin (dG) based room acoustic simulation scheme. The dG method is attractive for room acoustic simulations due to its flexibility and cost-efficiency. The porous material is modeled using an equivalent fluid model (EFM). The EFM formulation is validated analytically and experimentally, and it is shown that using the EFM leads to significant and perceptually noticeable improvements in simulation accuracy, when modeling single reflections and full room simulations with various types of porous absorbers.

Oedometric-like setup for the study of water transport in porous media by quasi-elastic neutron scattering.

In comparison to condensed matter, soft matter is subject to several interplaying effects (surface heterogeneities and swelling effect) that influence transport at the nanoscale. In consequence, transport in soft and compliant materials is coupled to adsorption and deformation phenomena. The permeance of the material, i.e., the response of the material to a pressure gradient, is dependent on the temperature, the chemical potential, and the external constraint. Therefore, the characterization of water dynamics in soft porous materials, which we address here, becomes much more complex. In this paper, the development of an original setup for scattering measurements of a radiation in the transmitted geometry in oedometric conditions is described. A specially designed cell enables a uniaxial compression of the investigated material, PIM-1 (Polymers of Intrinsic Microporosity), in the direction perpendicular to the applied hydraulic pressure gradient (up to 120 bars). High pressure boosting of the circulating water is performed with a commercially available high-pressure pump Karcher. This particular setup is adapted to the quasi-elastic neutron scattering technique, which enables us to probe diffusion and relaxation phenomena with characteristic times of 10-9 s-10-12 s. Moreover, it can easily be modified for other scattering techniques.

Elastic instabilities, microstructure transformations, and pattern formations in soft materials

Large deformations of soft materials can give rise to the development of various elastic instabilities. The phenomenon is associated with a sudden and dramatic change in structure morphologies. The underlying mechanism is crucial for the formation of complex morphologies in biology. Moreover, the concept of instability-induced pattern transformations is promising for designing novel materials with switchable functions and properties. In this paper, we review the state of the art in elastic instability phenomena in soft materials. We start by considering the classical buckling in beam-based structure lattice designs. Then, we discuss the instability-induced microstructure transformations in soft porous materials, and heterogeneous multiphase and fiber composites. Next, the mechanisms – often involving the post-buckling consideration – leading to the wrinkling and folding, creasing, fringe, and fingering are discussed.

Designing Sensing Devices Using Porous Composite Materials

The need for portable and inexpensive analytical devices for various critical issues has led researchers to seek novel materials to construct them. Soft porous materials, such as paper and sponges, are ideal candidates for fabricating such devices due to their light weight and high availability. More importantly, their great compatibility toward modifications and add-ons allows them to be customized to match different objectives. As a result, porous material-based composites have been extensively used to construct sensing devices applied in various fields, such as point-of-care testing, environmental sensing, and human motion detection. In this article, we present fundamental thoughts on how to design a sensing device based on these interesting composite materials and provide correlated examples for reader’s references. First, a rundown of devices made with porous composite materials starting from their fabrication techniques and compatible detection methods is given. Thereafter, illustrations are provided on how device function and property improvements are achieved with a delicate use of composite materials. This includes extending device lifetime by using polymer films to protect the base material, while signal readout can be enhanced by a careful selection of protective cover and the application of advanced photo image analysis techniques. In addition to chemical sensors, mechanical responsive devices based on conductive composite materials are also discussed with a focus on base material selection and platform design. We hope the ideas and discussions presented in this article can help researchers interested in designing sensing devices understand the importance and usefulness of composite materials.

Mode III fracture toughness testing and numerical modeling for aerated autoclaved concrete using notch cylinder specimen subjected to torsion

The aerated autoclaved concrete [AAC] is a widely used material in civil engineering for constructing masonry elements. It has excellent insulation and strength properties. The soft porous building materials during exploitation of engineering structures are subjected to various types of loading. The stress state in masonry elements are generated by thermal conditions, shrinkage, weight of other structural elements and service loads. In specific cases, the failure of these materials can be occurred due to out-of-plane sliding or mode III deformation. However, the mode III fracture toughness (KIIIc) of such materials has rarely investigated. In this research using a circumferentially notched cylinder sample subjected to torsion moment, the mode III fracture behavior of AAC (as a model brittle and soft building-material) is investigated experimentally. The KIIIc value was obtained equal to 8.201 ± 0.549 kPa m0.5 for the AAC with a nominal density of 700 kg/m3 that is significantly smaller than the mode I fracture toughness (KIc) of this material demonstrating the high risk of fracture under tear type loads. The laboratory tests were re-analyzed numerically. The results of the conducted analyses indicate that the numerical predictions of AAC under torsional loading conditions and based on the fracture properties assessed in the bending test allows predicting the mode III fracture toughness of AAC with an acceptable agreement.

Collective structural properties of embedded molecular motors in functionalized metal-organic frameworks.

Photo-responsive molecular motors incorporated in soft porous materials enable the amplification of the motion of individual motor units by employing their collective and cooperative behavior. Metal-organic frameworks (MOFs) provide in this regard, due to their structural diversity and modular assembly, a unique matrix to construct well-defined and systematically tunable molecular environments for the embedding of molecular motors. However, despite advances in the development of such photo-responsive functional materials, a thorough understanding of the governing interactions at the atomic scale has been missing so far, limiting the possibility of predicting and fully exploring the potential of these assembled machineries. Here, we present a conformational study to unravel the collective structural behavior and elucidate the impact of motor-motor interactions on the local and global properties of the scaffold. In particular, our work highlights the impact of full conversion of the embedded molecular motors on the overall network topology of the MotorMOF and thus acts as a benchmark for future studies to further explore the correlation of responsive building units with the resulting functionality of these hierarchical systems.

A Flexible Carbon Nanotubes-Based Auxetic Sponge Electrode for Strain Sensors.

Soft compliant strain gauges are key devices for wearable applications such as body health sensor systems, exoskeletons, or robotics. Other than traditional piezoresistive materials, such as metals and doped semiconductors placed on strain-sensitive microsystems, a class of soft porous materials with exotic mechanical properties, called auxetics, can be employed in strain gauges in order to boost their performance and add functionalities. For strain electronic read-outs, their polymeric structure needs to be made conductive. Herein, we present the fabrication process of an auxetic electrode based on a polymeric nanocomposite. A multiwalled carbon nanotube/polydimethylsiloxane (MWCNT/PDMS) is fabricated on an open-cell polyurethane (PU) auxetic foam and its effective usability as an electrode for strain-gauge sensors is assessed.

Drying kinetics and acoustic properties of soft porous polymer materials

We describe a method for the fabrication of acoustic metasurfaces, which is based on soft porous polymer materials. The materials are obtained using an emulsion templating technique, which allows for the fabrication of soft porous polymers with fully controlled porosity values between 0 and 30%. Our approach involves the polymerization of water-in-silicone emulsions with controlled water volume fractions. The obtained wet solid monolith samples are dried using three different methods. Due to the softness of the polymer matrix, and like in polyHIPE hydrogels or silica aerogels, the first method—regular air drying—leads to a collapse of the material and we present a complete experimental study of the observed kinetics as well as a model to account for the observed results. We show that this model can catch the kinetics characteristics. Then, using two alternative drying techniques, H2O2-assisted and supercritical drying, we show that it is possible to obtain materials with fully controlled porosities. The speed of sound—or equivalently the material acoustic index—inside the material being dependent on its porosity, we obtain a gradient-index acoustic material by spatially controlling the porosity distribution along the two dimensions of these metasurfaces. Their ability in terms of wavefront shaping is then demonstrated through a deflecting experiment performed in water with a sample having a thickness five times smaller than the incident acoustic wavelength at ultrasonic frequencies.

Three-dimensional reconstruction of porous polymer films from FIB-SEM nanotomography data using random forests.

SummaryCombined focused ion beam and scanning electron microscope (FIB‐SEM) tomography is a well‐established technique for high resolution imaging and reconstruction of the microstructure of a wide range of materials. Segmentation of FIB‐SEM data is complicated due to a number of factors; the most prominent is that for porous materials, the scanning electron microscope image slices contain information not only from the planar cross‐section of the material but also from underlying, exposed subsurface pores. In this work, we develop a segmentation method for FIB‐SEM data from ethyl cellulose porous films made from ethyl cellulose and hydroxypropyl cellulose (EC/HPC) polymer blends. These materials are used for coating pharmaceutical oral dosage forms (tablets or pellets) to control drug release. We study three samples of ethyl cellulose and hydroxypropyl cellulose with different volume fractions where the hydroxypropyl cellulose phase has been leached out, resulting in a porous material. The data are segmented using scale‐space features and a random forest classifier. We demonstrate good agreement with manual segmentations. The method enables quantitative characterization and subsequent optimization of material structure for controlled release applications. Although the methodology is demonstrated on porous polymer films, it is applicable to other soft porous materials imaged by FIB‐SEM. We make the data and software used publicly available to facilitate further development of FIB‐SEM segmentation methods.Lay DescriptionFor imaging of very fine structures in materials, the resolution limits of, e.g. X‐ray computed tomography quickly become a bottleneck. Scanning electron microscopy (SEM) provides a way out, but it is essentially a two‐dimensional imaging technique. One manner in which to extend it to three dimensions is to use a focused ion beam (FIB) combined with a scanning electron microscopy and acquire tomography data. In FIB‐SEM tomography, ions are used to perform serial sectioning and the electron beam is used to image the cross section surface. This is a well‐established method for a wide range of materials. However, image analysis of FIB‐SEM data is complicated for a variety of reasons, in particular for porous media. In this work, we analyse FIB‐SEM data from ethyl cellulose porous films made from ethyl cellulose and hydroxypropyl cellulose (EC/HPC) polymer blends. These films are used as coatings for controlled drug release. The aim is to perform image segmentation, i.e. to identify which parts of the image data constitute the pores and the solid, respectively. Manual segmentation, i.e. when a trained operator manually identifies areas constituting pores and solid, is too time‐consuming to do in full for our very large data sets. However, by performing manual segmentation on a set of small, random regions of the data, we can train a machine learning algorithm to perform automatic segmentation on the entire data sets. The method yields good agreement with the manual segmentations and yields porosities of the entire data sets in very good agreement with expected values. The method facilitates understanding and quantitative characterization of the geometrical structure of the materials, and ultimately understanding of how to tailor the drug release.